Big company jobs tend to be alike in many ways (due to their size), whereas startups vary so significantly that it's deceptive to think of all startups as interchangeable.
So yes, there will always be some startup opportunity available, but if you know that there are good people working at this one, or if they're working on interesting things, then I think it's a better option.
Doing it the other way around (try a startup, then go to BigCo) is less optimal.
I asked managers at Yahoo, Google, Amazon, Cisco and Microsoft how they'd feel about two candidates, both 24, with equal ability, one who'd tried to start a startup that tanked, and another who'd spent the two years since college working as a developer at a big company. Every one responded that they'd prefer the guy who'd tried to start his own company.
Another good point, between this and what ken said I think I'm leaning IBM now.
It's perfectly possible to go from college into a startup (or to skip the college part), but in general you will do better (and contribute more) in a startup when you have some experience in a large company. You may not want to retire from IBM, but it's good to see the good and bad bits about how a large organization is run.
The IBM job may or may not be there in another 5 years. There will always be some startup opportunity available.