Don't want to generate too much spoilerage here - so you may want to avoid some of my paragraphs if you don't want to ruin it as a player.
RotRL is more complete right now, and so you have the benefit of hindsight and full information to build the campaign. I think it does a good job of introducing Varsia, and by extentsion Golarion, to players - especially if you allow them to study the Player's Guide first.
Mechanically and geographically - it is kind of all over the place - Sandpoint is the focus for building the game, but your characters will travel parts of western Varisia (the main landmass for the adventures in Pathfinder so far) - so there may be a need to create additional details if they go off the beaten path of the main game. There's a Gazetter in PF#3 that does some filling in, but it's basic stuff.
From a role-playing standpoint, there's lots of NPC characters and the setup is tight enough - it being a small town - to allow for your players to sit down and chat with almost everyone if they like. Part of the series interest is giving your characters a place to call home.
Plotwise, and this depends on your players, you may find that it moves from traditional adventure to horror themes and back to more classic themes. There's an undercurrent plot that will develop into the main theme of sin and the Runelords as you move along. Still, depending on how much they learn, your players may be asking "why is it called Rise of the Runelords if there are no Runelords?" for the front half of the series.
Overall, I would say the ROTR series is a more open-ended story that allows for your players to expand what they know about Golarion.
CotCt's main problem would be in that it's just started. Normally, this shouldn't be a big deal - and perhaps for you it won't be - but experience has been that elements in the previous a previous Pathfinder storyline often remerge later with more information. So something mentioned in the first COTCT book may come back in a later issue of the COTCT series. I tend to be a completionist, and so knowing all I can about NPCs or events (as might be revealed in a later issue of the series) helps me better understand how to craft the adventures to players.
In ROTR, for example, the characters meet an NPC named Aldern - who just seems to be a simple plot device for the players to get some flavor for the town and world. In the next issue, it turns out he's a psychotic, murdering undead - and he's obessesed with one of the PC's. You can easily craft this on the fly, I guess - but if you like to plan ahead or at least know what PC to target from the start - then having all the PF information from the whole series proves beneficial.
A similar situation pops up with keeping track of "sins" the players commit as part of a dungeon they'll encounter in issue 5 or 6.
Setting-wise, most of the adventure is scheduled to take place within a large, metropolitan city - Korvosa. This allows you to minimize some mechanics, I think, as you can plan all your details within a certain framework. The Player's Guide and Guide to Korvosa books help establish the setting and give your players insights so they can develop their own characters with a feel for the game. This is supposed to already "be" home.
From a role-playing standpoint, there's also plenty of details and NPCs as well - more than you'll need I suspect - to help move things along and keep them interesting. In this sense, it might be argued that you and your players will need a little more "study" time to better frame their PCs personalities and motivation. Also, the initial plot ideally requires all your players have a similar motivation for starting the adventure - they really just can't "join" up and wander into the city - at least not without making some major start-up adjustments on your part. It's a great plot mechanic, but your group may feel it is too contrived.
While most of the mechanics are fairly straight, there's one thing that may require more prep-work than standard. This is the Harrow - a fortune-telling mechanic that is supposed to provide your players with a small bonus at times. It's a very cool thing and adds a great deal of color and mood; and it's not too complicated. But, you implied time management for you to set up would be limited, so I thought you should be aware of it.
Plotwise, and again this isn't complete enough for me to explain well, the storyline is that you need to save this big city from all sorts of perils throughout the adventure series. There's an underlying plot that involves the queen and what her true reasons for all these plans are - but before you get there it looks like you'll spend time on protecting the city and solving the mystery. The big concern that has been voiced by some people, - and this may extend to your players - is there enough characterization to make you "care" what happens to the city? There's enough indivduals that the PC's will meet that it may suffcient for them to believe they need to save them, but Korvosa as a whole may not inspire your players to feel like they are doing a good thing for "Queen & Country" as it were.
Overall, it looks to be a tighter storyline than ROTR. This can focus the adventure better for you, but you may find that the setting as a whole doesn't suit your players. It's an urban adveture compared to ROTR's more frontier feel.
Hope that was helpful...I don't know if I have covered everything in the most helpful way, but I tried to focus the critcal things that would relate to what you expressed in your original post.
Apologies if it rambles a bit much.
*****Addition*****
Player-wise, I forgot to add most of the PF's look like they are designed with 4 players in mind - although certainly 6 shouldn't unbalance things too much. You may find yourself adding/adjusting monsters or villains in either case to pose more of a challenge however.
As far as classes go, I think you can work with any set of people, but certainly it would be ideal to have at least one mage and cleric type. As for a bard character, I think he'll feel at home in either secnario. Korvosa, in CoTCT, seems to have a slightly better feel for a bard however - since it will present him with more opportunities to use his performance and personality skills with a greater range of people. Reference in the books even seems to imply that bards are highly appealing(and critiqued) to the citizens of Korvosa.
Also, keep in mind, that if you plan on using Alpha rules - they have only developed the main four - rogue, fighter, cleric, mage. So, anyone playing outside those may have to make changes as you play along in any adventure. Unless you plan on waiting for Paizo to release an update of Alpha that contains all characters?
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Also you said that your group likes Roleplay more than combat. Depending on how logical your group is, Some parts of RotRL have been cited as having monsters thrown together without much cohesion as to why. While reasons have been made on these boards you might have to dig to find them, and thus it may add to your prep time.
I recommend that even if you don't run RotRL, at least read the first grouping of encounters. CotCT seems to be a little more accurate (IE: less things are explained away to magic, and a little easies to relate to as a result) which could make role play easier in some respects.
No worries, mate - glad to help.
Hopefully, your group will have a great deal of fun! Good luck!