peek for the answer.
It doesn't pick your card at all. It shows you six cards, then shows you five different cards. It then tells you that your card isn't one of the five cards. Of course it won't be since none of the first group of cards are there. Test this - do the test and pick ALL the cards - you'll notice that the test gets it 'right' even then!
It plays on the fact that face cards are all relatively similar to one another and the participant just assumes the second group of face cards represent the cards they didn't pick. If you make the test more obvious, its trick is plainer. Here are three colours, pick one of them:
Red, Green, Blue
OK, now I'm going to remove the colour you thought of:
Purple, Orange
I'm willing to bet that I managed to 'pick' your colour out of the list!
Edited by Modulous, : No reason given.