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To quote myself, "Backstory is not done via classes. PC classes aren't about mundane activities, they're about adventuring (with a big focus on fighting), everything not relevant to adventuring should not be represented by class levels."
The Traveling Merchant NPC in the GMG is an expert, exactly because mundane professions aren't represented by PC class levels.
Anyone with Appraise, Sense Motive, Diplomacy, and Bluff skills can be a competent traveling merchant. But classes with Charm Person, Suggestion, or other types of Seduction and Rogue-ish Silver-Tonguey-ness will excel though. Bard is probably your best option tbh.
If you're going to take the whole "Traveling Merchant" thing seriously, you should put skill ranks in Profession (Merchant) and you can use this as a passive sort of income. Basically, every week you roll a Profession (Merchant) check, and then receive half your total result as free GP. You have to tell your DM that you're going to the marketplace to buy and sell goods during your downtime, though.
Also, having a reputation as a Merchant can get you into a lot of places that you normally wouldn't be allowed, such as an invite-only party at the corrupt governor's mansion. A few days before the party, you could start rumors that you sell the finest minx furs on the continent and ensure this rumor finds the ear of the mansion guards, and then fabricate "the best Minx Fur shawl ever", and bluff your way past the guards saying that you're there to present the esteemed Governess with a once-in-a-lifetime "exotic gift", and then you can sneak your party members inside once you're in... or maybe you bluff the guards again into believing that they're your assistants... or something.
An inquisitor of Abadar might well pose as a travelling merchant and be good at it. Well, at first level they might well be a travelling merchant.
Even better, an Oathkeeper Inquisitor of Abadar can be a frighteningly good merchant. There's not many 1st level characters that has their deity act as the arbiter for trade contracts.
A negotiator bard would make a very effective merchant.
Being able to impose a penalty on his opponents appraise skill and to control the direction of the mistake is a huge advantage. The fact the margin of error scales up as the bard levels up makes it even better.
Gaining half your level on bluff, diplomacy, intimidate, knowledge local, and sense motive is a definite advantage to a merchant. Being able to take 10 on these skills will also help, but being able to take 20 without spending extra time is where the real benefit is. Sure they are limited in the number of times per day they can do that, but when you really need to make the roll you will.
They also get rogue talents several of which can be very useful to a merchant.
Their spell list includes a lot of divination, enchantment and illusion spells. They also get a lot of buffs including early access to heroism. That is a +2 bonus to all skills and save that last a long time. That is going to be very useful for a merchant.
I played a Gnome Chururgeon Alchemist as a traveling merchant (THIS GUY). He had 14 CHA, and a trait to give him Bluff as a class skill. I also rocked my bluff checks every time I rolled them, so even though my bluff checks weren't that great he got away with metaphilorical murder.
The archetype was basically so that I could ignore the Infusion doscovery for the first few levels, but wasn't really important otherwise. It's worth noting that Alchemists are only 4+INT skills per level, but as an INT-based class they'll out-do most non-INT 6/level classes pretty quickly.
If there are any classes that get bonuses from the Profession skill then they'd probably be a good bet, but I don't know of any.
Besides that the Bard is basically always going to be a good bet, but I also think an Occultist would make a good merchant of unusal oddities.
And of course the master-crafter that is the Wizard would be able to craft things better than most.
But honestly, as Derkl9rd said any class could be a merchant. Even a Fighter with no ranks in Profession, Appraise or any other relevant skills could do it - maybe they've gone adventuring because their business went bust?
Here's a side question: how do you manage this PC's merchandise?
Do you give it a free wagon, 2 horses, and 10,000 GP worth of goods, or would you have it start as an apprendice that build its inventory over time?
Wizard or Arcanist for early access to Teleport getting you to the Metroplises (metropoli?) that much faster... though Boots of Teleoprtation work for anyone.
Shrink Item on custom built wood crates could handle mundane item transportation needs.
Planar Binding line can get access to Mercane outsiders.
Ultimate Campaign book for info on running a general store.
Gun Smuggler Rogue going into Twilight Talon... between Stolen Shots and Dead Drop, you should literally always have something to sell, or at least know how to get it... take Leadership for a crafting Cohort, and make a supply chain out of your followers.
Gear Gnome Druid VMC Cleric [Brigh]... uses Druidic Herbalism and Divine Alchemy to produce a near endless supply of Potions. Take the Voice of Solid Things trait to put Craft on Charisma, since VMC Cleric gives you Channel based on Charisma... you can sell Channels, too.
Brigh's 3rd Exalted boon, Inspired Crafting, allows you to cast Fabricate 1/day as an SLA... so you can just manifest things to enchant and/or sell.