Here's my idea of a very optimized Fallout 1 build for a vanilla kind of playthrough.

An exotic alternative would be a high luck build that pumps all the skill points into gambling until you can consistently come out ahead at casinos. Then you go into a casino, hit the enter key to gamble until you have a ton of caps, then go and buy all the best gear possible and absolutely stomp the early and mid-game quests. Very fun to do with an energy weapon combat build.