Without any context, it's a bit hard to know what it is you are trying to say.
In the first one, you are using the emphatic "did" which stresses the verb. Therefore, "Who did pay for you?" sounds like there was a situation where someone couldn't pay a bill and the person asking never knew what happened until finally one day realizing it he says "oh yea! About that.. who *did*pay for you, because I never found out". Your second example is a more direct question, using the indicative, simply asking the question of who paid for someone's bill/ tab.
I hope that helps.