Are there startups already looking at this problem? If not, why not? And, who's up for a challenge?
The problem is the software and the software is not going to go away. The opportunity is to make the software more intelligent so that the output is more in line with what would work.
Not to mention the cost you could get for the unemployed to sign up ("It costs you on average 2k/month not to use our service").
I do think that this problem is up there with world peace.
I mentioned it in another comment already, but this problem is what I'm tackling with They Meet You (http://theymeetyou.com). At a minimum, I'll be using it where I work, but check it out if you want.
How it works is really simple: You can send a message to anyone that proves they work for a company, if you interest them then they can share their contact information with you.
The biggest problem I see in hiring people is that good resumes get filtered out by HR departments because the resumes don't have the precise keywords. Fix that by hiring smarter HR people.
In general, people aren't qualified to do their jobs. That doesn't mean they shouldn't be doing them, or be hired to do them. It means the qualification system is broken.