The Columbia MBA who becomes the VP/Finance of your dopey startup (instead of going directly into the smoke-filled rooms and half-million salaries) is going to have a gigantic chip on her shoulder, guaranteed, because she had to be in the bottom 5% of her class to be there.
If you want to be an attractive candidate for startups, and you have an MBA, first you need to succeed on the MBA track for a good 5-10 years, then you need to make a credible case that you've genuinely decided (after a few wins) that you want to take your life -- and that you're not just some carpetbagger who failed out of "real business" and is using the startup world to get a second chance.
Also, I have to agree that business people in startupland massively overvalue themselves. I'm a Tech 8, which means that if I'm looking for a CEO co-founder, I'm looking for a Business 8 (or 9; but since they generally have better negotiation skills, that match is almost impossible for now). I'm not going to take a subordinate role (and 2% equity) to a Business 6. If you're not coming to me with the resources in hand (funding and first clients already lined up) and you're not on a first-name basis with the top names of Sand Hill Road, you're not a Business 8. A Biz 7 comes with resources in hand and can get any article put into credible press; a Biz 8 can make any introduction in the world happen.
To tell the truth, though, Business 8 startup founders are exceedingly rare. They're usually venture capitalists.