As someone thats' just finished going through a job search, one of the biggest turnoffs that I found was companies that made you jump through hoops to even get to the interview stage. Whether it was dealing with recruiters (who with few exceptions were not worth the time to talk too), annoying applicant sites like jobvite or telos (my personal fav...not), or having to give your resume through their homerolled system that never parsed your resume right and you had to bring it with you anyways to the interview, it does nothing but sour people on your company. Doubly so for folks that are looking to get in on a startup.
A startup should be hiring themselves, they should be meeting with potential applicants themselves, and they should realize that people that are looking at startups are usually doing so because they DON'T want the trappings that the megacorps have. Throwing up barriers right at the offsets will scare the A and B level talent away to your competitors, and all you'll find is the C level talent, and the megacorps leavings.