You would look for the same thing in a snake you would look for in any other animal you want to buy: alertness, clear eyes, unlabored breathing, perhaps some curiosity if the snake doesn't seem overly shy - tongue flickering, coming out of its ball... If you're getting a baby, make sure they've shed out and eaten at least a few times - you're not going to want an unstarted baby as a first-timer.
If the vendor seems shady, walk away. If you get a bad feeling about the breeder or the snake don't be afraid to walk away - a good deal is often too good to be true, so be wary.
Also I would have your enclosure ready to go before you even head to the expo. You don't want to bring your new baby home only to realize oh no, their hot spot's too cold/hot and there's condensation inside and they can't go in to settle down until you get it figured out.
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