Startups should realize that this is a thoroughly idiotic notion, and should abandon it ASAP. The one thing that large software companies do well is SHIP PRODUCTS. A good software engineer is someone who can ship a product, even if its ill-defined or not feature-complete. This is a virtue. Small companies, especially startups, have a horrible track record for shipping software that in any way resembles its product plan.
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.
Which large companies have you worked for? I've worked in both environments and seen way more failed projects on the enterprise side.
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.
The big problem I see with this idea is that scrappy, do-whatever-it-takes people almost never write clean code, checkin cleanly, test properly, and practice good product design. I value these things more than "rugged individualism". Furthermore, if your software team is doing sales, that's a really bad allocation of talent. Even the tinyest of startups should have dedicated roles for the other dimensions of your business (e.g. Sales, Support, HR, CTO). You pit 2 teams against one another with the goal of producing a great product, and one team has a wide spectrum of talent, the other has great software engineering discipline, I would bet on the latter team every time.
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.