I'm generally speaking the retro-gaming guy around here. So it's my job to point out all the classics. By which I mean, the ones you shouldn't avoid because they're actually good. I'll try to avoid pointing out anything I assume you all already know about (No, I'm not putting Fallout anything on the list, although I did get both the originals and a few of the new ones, and they are on sale). So... here goes.
-Baldur's Gate - Actually, don't buy this. Well, don't buy it on Steam. Baldur's Gate is a classic, and it's the game that earned BioWare its name. However, the version on Steam is the "enhanced edition" which has garnered mixed reviews because it apparently alters the writing. As of this time, there is no good way to buy the original Baldur's Gate from Steam or GoG. Pirate it, or grab a secondhand DVD copy (which is what I did: they're pretty affordable).
-Planescape: Torment - This time around, the people who did the Enhanced Edition did good. So you can buy this on Steam or whatever, nice and easy. Apparently they caught on that a game that is beloved and revered, largely for its writing, doesn't need alteration on that front.
Planescape: Torment, like Baldur's Gate, is an oldschool CRPG-type game. It's an I-hope-you-like-text sort of game, so be warned. But if you do like text, the writing is well known for its strength. Also, notably, this is one of the rare old CRPGs which you can apparently get through without ever using combat. So... that's a thing.
If you liked Wasteland 2, Pillars of Eternity, or Fallout: New Vegas, you should probably know that Obsidian Entertainment and InXile were both formed by ex-Black Isle Studios developers, who worked on this game, Fallout, and the aforementioned Baldur's Gate. So... yeah.
-id software woooo - TL;DR, Thoth loves id software. Go buy Doom, DOOM, Quake, or whatever. Then go download a modern sourceport, and if you bought Quake 1 or 2 look up how to enable the soundtrack.
-Eidos - Basically, every single Eidos game is dirt cheap right now. That means all the Tomb Raiders, all the Just Cause games, and so on. Go go go go go.
-Looking Glass Studios - Yes, these are in the Eidos category, but they get their own listing. Because Looking Glass Studios deserves it.
Looking Glass Studios, for the uninitiated, is one of the most influential developers of the 1990s, and a pioneer of 3D games. Not all of their games are available on Steam, but their Thief series, a pioneer of first person stealth, is. As is System Shock 2, which really should need no introduction. And speaking of looking glass, $1 can also get you...
-Deus Ex - widely considered one of the best PC games ever released. It's a bit fiddly to get running on modern systems, so to recap what I had to do:
1. Select OpenGL as the renderer, no matter if the game tells you it's "unsupported". The game lies.
2. Open the game's folder on Steam, open the file DeusEx.ini in the "System" folder, and under the section "[Engine.Engine]", add a line that says "FrameRateLimit=60"
Yeah, it's a pain. But the game is good.
-Another World - A great adventure game-ey thing. But you may have to look at a walkthrough once or twice, and you will die. A lot.
-X-COM - Any of them.
-Xenonauts - It's classic X-COM with a fresh coat of paint.
-Civilization - Every Civ game is brilliant. Pick your favorite, but Civ IV is the cheapest one right now (7.50 for the full game with all expansions).
-Frozen Synapse - not a classic, but a dang good game. There's a demo, so you can try before you buy.
-FTL - Another non-classic, but it's the archetypical roguelike and if you don't own it already you should go buy it.
-Strife: An obscure Doom-engine FPS, it had RPG elements before it was cool, had an overworld you could freely explore, an actual story and quests and stuff, and was generally both fascinating and ahead of its time. The Steam version is updated for modern systems, with nicer graphics, better controls (I think), and a ton of content that was left on the cutting room floor in the original release. It's fun.
That's it for now. I'll probably think of something as soon as I post this, but whatever.