About Sid's bundle
Civ 3 complete is an enjoyable game, but it might be a tad too old for new players. It's still perfectly playable, no worries with that. Unfortunately for 3rd game 2nd and Alpha Centauri were better and that's how I remember it, it came after good ones
Civ 4 is great, really it is, it uses spies the way I prefer it, it had religion implemented in a nice way. As you get complete edition with bundle, you get the definitive version of a game. If you never played Civ, 4 is a good one to start with. It has fully automated improvement building (although I prefer manual in any civ), but it's good for new players, I guess.
Ace Patrols, I already wrote about them in steam thread couple of times. These are much simpler games if you compare with Civs, but training your pilots and keeping them alive can be fun. Also it doesn't require much time, unlike Civs, as missions are short.
Railroads! There is not much to say there, some people are into trains, some not. I vastly prefer Railroad Tycoons myself. Then for the fairness of it, I haven't played much of it.
Civ V. This one doesn't need much telling, it has so much content it can be overwhelming, but I think it's the best entry to Civ for new people in this bundle. I do prefer stacking ten thousand units in one spot myself, so I may be not one to tell about this game. Too many features are not the way I like, but it's as addictive as any civ, rest assured.
I would advice against playing vanilla though, you need expansions, both of them, in my opinion.
edited: forgot most important part, it's a great bundle, buy it! and play them games.