Starting with new people can be tough, since you don't know what kind of game they want. If their experience with RPGs has been video games then I would expect a more kick in the door style of gameplay would be something to their taste. I would say keep it simple at first, everyone’s first character is definitely not optimized the way their later characters will be. So I think their first few encounters should be interesting but not deadly, goblin raid on the harvest festival sort of thing, remember Goblins in pathfinder are almost comically stupid (After playing through the Rise of the Runelords campaign the chant of "We be goblins, you be food!" usually gets said in any encounter with goblins in my group).
I would talk to them and find out what kind of game they want, do they want a game that is more about the crunch of things (fights and looting) or about roleplaying. I would certainly add in some of both. I would also find out what classes they are planning to play and put some things in for every person to be good at, got a fighter with a great sword? Room of smaller enemies where power attack and cleave can really shine. Wizard? A harder to hit creature that magic missile would be effective against or a puzzle involving some arcane component. Rogue? Some traps for him to disable or turn against the bad guys or a chance to get the drop on someone. Cleric? Undead!
You get the idea.
Since you will be playing online I would think that it is going to be hard to keep people’s attention, especially if you have a spell caster since reading spell effects and understanding how they work can be hard for first time players. This can cause one player’s turn to take up more time than it normally would (and druids always seem to take up twice anyone else because of the animal companion, spell casting, and wild shape) and people are easily distracted, especially if they have the internet on hand. (I have trouble with my group surfing around on the internet on their iPods during my game if things get slow) This can cause some people to miss important details then get frustrated with the game as a result.
Are you planning on following an adventure path or doing something homebrew?
don't be afraid to limit what the players can take, i have a standard rule of newbies only being allowed to play fighters until the understand the flow of the game. fighters have simple things like additions to damage and hit and not a lot of things to remember.
but if the whole group is newbies my suggestion is limit them to the base classes (fighter/wizard/rogue/cleric) with the more reliable player(s) playing the casters.
Regarding wizard's I would recommend they take a look through Treantmonk's Guide to Wizards.
Make sure you're players are aware of www.d20pfsrd.com
don't be afraid to limit what the players can take, i have a standard rule of newbies only being allowed to play fighters until the understand the flow of the game. fighters have simple things like additions to damage and hit and not a lot of things to remember.
but if the whole group is newbies my suggestion is limit them to the base classes (fighter/wizard/rogue/cleric) with the more reliable player(s) playing the casters.
Although I usually suggest that people who are new to the game pick something simple (usually this means basic fighter or a cleric and let me map out their spell list until they are a little more familiar with the game.) I don't usually go so far as to force them to pick something simple. I just let them know that the game has some very complex situations since the basic rules are simple but every ability and spell is some exception to the base rules.
I do think the spellcasters will be the big stumbling block. If they are an arcane caster it is not too big of a problem because you can just look at their spells known before the session and then read those so you are familiar with their effects. Divine can be a bit trickier since their spells known can completely change day to day. Hopefully though before spells start becoming too complicated they will have the hang of it (this usually starts at 5th level as far as i've seen)
In my experience new players tend to focus on spells that do direct damage, since they might not know that color spray is a absolute killer at low levels they may opt to go for simpler spells. To keep things simple you might suggest a universalist wizard for someone playing their first time through to help avoid some of the trickier spots of specialist wizards (though these are easier to navigate in pathfinder than they were in 3.5)
If you come to a point where you don't know an answer and can't find it quickly make a guess to how it should work to keep the game going but let the group know that you will research a more official answer after the session and have an answer before the next session. This may lead to some inconsistencies but it stops the game from pausing every 30 minutes for rule clarifications.
If you and the players research the game well enough then you should be fine. Make sure that everyone knows the different types of basic actions (full, standard, move, swift, free) and how attack and skill rolls work.
Like I said before keep it simple and introduce new concepts into the game slower (once players are comfortable fighting standard goblins then maybe a hobgoblin shows up and makes some trip or grapple checks to introduce CMB/CMD). Once the basics are in place you can start adding in more interesting things.
There are some advantages to playing with a group of new players though, when you describe a creature like this:
The creature looms before you, it's protruding jaw dripping with drool, green fur covering it's tough hide, hands large enough to grasp your head end in razor sharp claws.
The party won't immediate scream "it's a troll, kill it with fire!"
Is there any specific section of the rules that you think you need to brush up on? If so I would highly suggest at least giving it a passing glance.
*Edit*One more note, Paizo will be releasing a guide for GMs soon but if you cannot wait the DMG II for 3.5 has some great advice on how to navigate behind the GMs screen.*Edit*