You have to ask yourself if you couldn't gain better experience by a) working for a big company b) going to grad school c) founding your own startup. There might be cases in which the underpaying startup job really is the best next-stage career advancer. Even if this is true, read any non-compete agreement very carefully. I've had people shove non-competes in my face before telling me what the company actually did (so I could not compete with the entire industry? No thanks).
I would also not go in assuming that the company will be the next Facebook. Find out how the founders and investors plan to exit, and decide if that's acceptable to you. Furthermore, make sure you can deal with failure.
I think going in with realistic expectations and a clear head is just as important to the startup one wishes to join. I suppose there are some startups (many in NYC) whose goal is to suck in naive techies and dump them when they burn out, but most probably want to build a real team. If you sign something based on unwritten expectations, you are setting up for resentment and conflict when those expectations go unmet.
I probably sound overly pessimistic now, but I don't mean to be. Joining a startup can be a great opportunity in innumerable ways. I still intend to launch, even after some of the worst months of my life. Many of my friends who shared this sentiment no longer do. I think some had naive expectations about the lifestyle, how quickly we'd all be rolling in money, and what being an "entrepreneur" would look like to the rest of the world.