It also doesn't hurt to go back later and try to understand why you had the gut feeling that the person is an asshole. Knowing what sort of cognitive biases you may have, either from instinct or socialization, will likely help the false positive rate. And the more you are considerate about things, the less you might be likely to come off as a prejudicial asshole to someone else.
Personally, my snap judgements seem to be pretty reliable. Many times I've taken an instant disliking to someone, while other in the social group found the opposite, when months or years later the person will confirm my suspicions by involving themselves in some big scandal or something.
I think knowing when and when not to trust your intuition is a big part of the intuitive process.