Alternatively, working at a startup may not have the same cache when not in the Valley, but you might get a chance to work with some awesome tools that are ahead of the curve that would get you experience for a future job.
I think it totally depends on what you do there. I'd probably hire someone who has the full gamut of dev, sysadmin and customer interaction experience from a startup. Less so if they couldn't effectively describe how they'd helped get the business running.
> working at a startup might not have the same cache ...
I've co-founded companies in Boston, NYC and SF and I've also worked at large software companies. I've seen quite a bit of appreciation of startup talent in all cases.