The point of Blink is that gut calls are remarkably accurate when made by an expert with significant pre-existing knowledge and experience in the field. By letting your unconscious make the decision, you can tap into all the knowledge that just doesn't fit in your conscious mind. The brain's basically a massive pattern-recognizer: gut calls are effectively patterns bubbling up into your subconscious that rely on some deeply hidden information.
Gut calls fail terribly when made by people with no expertise in the subject. Blink gave the example of Warren G. Harding: he fit everybody's preconceived notions of what a strong leader should look like, but he was an idiot. George W. Bush is a more modern example. Every time you suffer buyer's remorse after an impulse purchase, it's your gut letting you down.
Every entrepreneur needs to realize that hiring is inherently a low-information process. You don't know anything about the person applying for the job. You can convince yourself by gut call that he's a good fit, but you're as likely to be wrong as right.
The real best way to hire is to have the person work for you for about 3-6 months as a contractor or intern first. Then you go based on your intuition. After 3 months, you've got a stock of information to make a good gut call. You've worked with them daily. But you can't just expect your intuition to magically work in your favor, no matter what.
Although Blink does present the dangers of gut calls, you seem to agree there is really no other alternative when it comes to hiring. As an entrepreneur, almost every call you make is made with an element of inconclusiveness. Almost every call is a gut call.
Some gut calls do fail terribly, but when the only way to get the experience and pre-existing knowledge to make the call is to make a few mistakes, you're SOL.
Catch 22, I guess! :-)
Actually, it does. Read Blink: http://www.gladwell.com/blink/ by Malcolm Gladwell for a better idea of this.
I can understand that you're looking for something more cut and dry, but it just doesn't exist. If you've got a problem trusting your instincts, you are probably going to have issues with business decisions in the future as well.
If you want my advice, your first hire should be someone with a track record of making good gut calls, to balance out yourself. That's all I'd look for really - well, besides the need to work well with you. Let him/her hire the people you need, and stick with the analytical stuff that he'll probably hate to do. :-)