What really sucked me into full-time PC gaming was Garry's Mod. Pick up CS Complete and Garry's Mod and play some of the online modes (Trouble in Terrorist Town, Zombie Survival, DarkRP).
Some good games to try if you haven't played anything on a PC before:
Crysis (series)
Starcraft (series)
Any Valve game (Counter-Strike, Left 4 Dead, Half-Life, Team-Fortress 2)
Planetside 2 just came out and it's a good representation of what's to come.
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