Just signed up -- great idea!
Small problem: I clicked the "Get Startup Help" button, selected an area of expertise, and was then paired with someone. The random selection (instead of being able to browse available profiles) is not necessarily a problem, but now I can't cancel my request for help...
Also, it would be great if you sent out emails when you were paired with someone else -- a sort of automatic introduction. Do you send out an email to the person that was paired? Hopefully -- as I won't necessarily come back to the site to check if I have requests waiting for me.
Finally, perhaps the global list of users could be augmented by a bit of geographic info -- just to see if someone's close to you (might be nice to meet fellow hacker buddies)?