Joining a startup out of college is not hard. As I grew up, I went through the educational funnel to these types of jobs (McKinsey, Google, etc) and I found myself disliking the people around me and (especially in the case of finance / manage consulting) disliking the work they were going to dedicate their lives to. So I just never applied to work at companies I found distasteful. It was quite easy.
But you didn't straight out of college, which is my point. I am in the same boat as you.
I don't think your solution will work. The people who should join startups don't prioritize brand value or the alleged security of working for a big company. They may prioritize compensation - but the startup world already answers that problem by allowing you to choose where on the risk scale you want to be (you can always start your own company if you're like me and very interested in compensation).