If I was starting out on this game, what would be a good character to use and how would I get used to playing on a pc after playing Xbox all these years?
If you were pretty good in the Orange Box, I'd say you'd have no problem whatsoever, class-wise.
However, you do need to read up the
Team Fortress 2 Wiki pages on weapons and learn what they do. As of right now, there are somewhere around 80+ different weapons, not counting re-skins.
In terms of maps, there's a ****ton of different game modes available, official or not.
I'll try to explain as best as I can
Medieval Mode: Pretty straightforward, the only weapons allowed are ones that could have existed during the Medieval Ages. So pretty much, no guns and sentries. I think the only official map released so far is cp_degrootkeep
Mann vs. Machine: It's a mode where teams try and survive wave after wave of robots. You can upgrade your weapons using the credits you earn from finishing rounds and killing robots. The upgrades are restricted to Mann vs. Machine only. Maps that begin with "mvm_<map name here>" is for that mode.
Territorial Control: Pretty straightforward, teams fight for territories in the map. Don't play this unless you're masochistic because it's really, really long and time consuming. Only fun in 32-man servers. Maps are tagged with "tc_"
King of the Hill: One control point. Two teams. First team that holds the hill for a combined time of 2 minutes win. Maps are tagged with "koth_"
Arena: TF2 Team Deathmatch. Maps are tagged with "arena_"
Payload: You must push a bomb from the starting line to the end within the time limit. There are checkpoints that you must go through to extend your time limit. The opposing team is supposed to stop you from doing so. A derivative of this mode is Payload Race, which is pretty much the same thing 'cept that both teams are pushing bombs from the opposite sides of the map and you have to get to your point first. Maps with "pl_" are for regular Payload, while "plr_" is Payload Race.
Versus Saxton Hale: This is pretty much Boss Fight: The Game. You fight a boss, usually Saxton Hale. Boss is extra powerful and tanky. This is an unofficial mode. Maps are tagged with "vsh_"
Zombie Fortress/Super Zombie Fortress: Pretty much Left 4 Dead TF2 style. Unofficial. Maps are tagged with "zf_" or "szf_"
Prop Hunt: Every round, each team gets transformed into a stage prop. and you must hide and survive within the time limit. Pretty much TF2 hide and seek. Maps are tagged with "ph_"
Achievement/Idle/Trade Servers: This is a server where there is no objective but to farm achievements to unlock weapons faster. You can also leave your game overnight in these servers to get drops, as well as trade with others. Not even a game mode. Maps are tagged with either "achievement_" or "trade_"
There are a lot more unofficial game modes like jump maps ("jump_"), dodgeball ("db_") and Balloon Race. Just peek at servers.
There are 5 ways you can get weapons.
1. Drops: For every hour you play, you are eligible for a weapon drop, for up to 8 drops a week. This cap is reset on Wednesdays, and leftover items are carried over the following week, upto a maximum of 16 items. If you're lucky, you can drop a hat instead of a weapon.
2. Achievements: You do achievements for each class, and for every Achievement Milestone you unlock, you get 1 weapon. These weapons are bound to you and are untradable. It's best you do these first.
3. Trading: If you're well off in TF2, you can trade. Simple enough. You have what he wants, he has what you want. You can only trade if you're a premium member. To be eligible for premium status, all you have to do is buy something from the TF2 cash shop, and it could be anything, even the $0.49 weapons. Read up on the TF2 economy if you don't want to get ripped off on trades, or don't if you don't give a rat's ass about trading and want to just play the game.
4. Crafting: It's mainly used for making fancy promotional weapons because everything else can be obtained through trading/idling.
5. Open crates: Once in a while, you drop a crate. These are locked, and can be opened with a key. A key costs $2.50 in the cash shop. There isn't anything gamebreaking in these, just vanity weapons that count your kills. That's it. Completely optional too. The only crate that's valuable is somethign called "Salvaged Mann Co." crates. If you get one, extort as much as you can because these are pretty rare.
I think that's about all I can tell you about TF2.
Oh, and yearly, TF2 has Halloween and Christmas events. Tons o' fun.