Neither undergraduate college has been a launching pad for political careers. The only prominent politician whom I know of who graduated from either as a undergrad is former and now disgraced governor of Connecticut, John Rowland (Villanova).
Where a politician obtained an undergraduate degree is largely irrelevant to their success. Hopefully our political leaders are smart and knowledgeable. You can become well informed and well educated at either of these schools. Compare the departments of political science at the 2 schools. I think Villanova’s is particularly strong? Villanova seems to have a more extensive study abroad program (I could be wrong, so check) and developing an understanding of international affairs could be a helpful background in government. Because of the success of its basketball program, Villanova has higher name recognition among the general public outside PA right now, for whatever that’s worth.
To me, the critical questions have to do with why you want to go into politics/government in the first place. Where do you want to make your mark? What kind of public service do you want to do while you’re an undergrad? What area of expertise do you want to develop? (Many politicians have a special interest area for which they advocate and are knowledgeable about.) What is your passion? What are your leadership skills and where do you want to lead people? Politicians neeed to be knowledgeable about business and economics. How does that fit into your vision?
When you can answer those questions and others like them, the choice of college may become more clear. Those answers will describe what you want to get out of college, and then you can see which of the two schools can better prepare you in those areas.