I'm fortunate in as much that my professional accreditations (and being a part time student) get me access to all sorts of discounts, but even still it's worth asking for a student discount (or whatever they offer at the till) all the same.
Nine times out of ten, the retail staff aren't paid enough to give two fucks, so they'll just put it through as whatever discount appears on their till.
The worst they can say is no, after all - and that costs nothing.