The Madman said:
Listen to this person as he speaks the truth. On top of these, I'd recommend the following:
Crysis - Despite being 3 years old, this game still looks fantastic compared to pretty much anything on the market (even its own sequal). Combined with a unique environment and wide open levels, I honestly can't think of a better PC exclusive to give your new rig a work-out with.
Dungeon Keeper 2/Startopia - I've combined these 2 as they both offer a similar experience. They are both an interesting spin on the traditional management sim as well as having a great sense of humour about them.
Freelancer - I just like trying to get people to play this as it introduced the idea of using your mouse for flying in a space sim. Surprisingly, it works and I hope one day it will ressurect a dead genre. On top of that, its a fun and very open game.
Black and White 1/2 - The game that gave Peter Moleneux his reputation for promising more then he could deliver and is probably the poster child for "Brilliant ideas, poor execution". However, if you can work your way past its flaws, its a very fun game (though a pain in the arse sometimes) and its worth picking it up cheap just for the experience.
The Witcher - An RPG with no Good or Bad options, just actions and consequences. While the combat is a bit lackluster, play it for the story and weep as you realise how Bioware are holding back story telling in RPGs.
Vampire: The Masquerade: Bloodlines - The game with 2 subtitles. Buy it, patch it, love it! (Though avoid Malcavian or Nosferatu on your first playthrough as they make it much harder)
Also, now that you've joined the ranks of PC gamers, you can enjoy the RTS genre as it should be played. I would recommend the following for non turnbased fun:
Age of Empires 2 - AoE2 is your "Classic" RTS and the game that refined the formula that would define the genre for years.
Rise of Nations - Takes the AoE formula and adds a world conquest map for more objectives and purpose.
Sins of a Solar Empire - The scale will either make you fall in love with it, or have you running away screaming.
Supreme Commander - Small maps, MASSIVE UNITS!
Dawn of War: Dark Crusade - This is the one I'd recommend to beginners as its easy to get hold of, cheap (especially on a steam sale) and will help you learn the RTS basics. The unit variety between the different factions also means there's sure to be at least 1 side that suits your playstyle.
Any Total War game - While I'd avoid Empire (guns make war boring) these games do a great job of combining the micro-management of battle with the macro-management of your kingdom. Pick a historical period that matches your interests and have fun.
World in Conflict - A game you hear little about, but was a bold venture in both storytelling in an RTS as well as changing things up from the traditional base building & resource gathering of pervious games. If you find other RTS's on the list a bit slow going for your tastes, try this instead.