At my startup, candidates from large companies are immediately prioritized in the hiring queue. This strategy has always paid off; there is a high correlation between large company experience and good software engineering practices.
However when an enterprise ships something, the shipped product tends to be more stable. There's tradeoffs to be made and large companies often prioritize stability and their reputation over time to market and spending money.
As a startup, I would look for people who have less specialized experience and are able to cover as many of my bases as possible. Can the developer field a page at 2am and login to the production environment to fix a problem? Can the developer help my sales people with a desktop support issue while the lone IT guy is on vacation? Can the developer make the product work on a single AWS micro instances until we get some sort of traction/funding?
The theme here is a scrappy, do-whatever-it-takes mindset that's often missing in the enterprise where people learn to CYA lest the bureaucracy come down on them for cutting corners.
Definitely aware of several hot startups that don't seem to value this at all. Well it's a tradeoff that they are hopefully consciously making.
If startups are so opposed to big companies, shouldn't having these on your resume be seen as being negative?