From what I have seen, the only validation that you can currently do is whether it is required or not. I earlier recommended that they add in the ability to do a Regex validation on a custom filed. To do a database validation would be more involved, but you could request that feature be added.
I have customers that need to supply a serial number in order to purchase a software upgrade. I made a custom field for the applicable products and made it required, but the customer can enter whatever they want. We have to validate that serial number when we get the order. If they do add that feature, I would be interested in it. If they at least added a Regex validation, the customers couldn't just enter any old value.