I think both have their advantages, if you notice a lot of rich guys like Trump, or Richard Branson aren't that good looking but have been with some very good looking ladies. But you really can't do anything about the way you look no matter how much money you have. If you were poor and good looking, most girls don't want poor guys, and it depends on how poor and why you are poor. Are you just down on your luck, or did you make bad choices and don't have any education and will probably be poor for a while? Either way you won't be poor forever, and you may even become rich one day, and you will always look good. Realistically I'd like to be in the middle, but for the sake of the question I'd be poor and good looking.
It depends how rich and how good looking, but I think I'd go with rich. I've always wanted to build a 7 story high tunnel thing like you see in McDonald's playplace or Chuck E Cheese's. That's gonna take some dough.