If you buy new decals from a reputable source, then you assume they are fresh. And if they aren't, you return them for an exchange when after you find the problem.
With NOS ones, unless the decals are separating from the backing paper, you don't have a way to tell if they are any good until you try installing them.
The first shop that had my car said they wouldn't even attempt to install NOS stripe decals. He'd had a bad experience installing NOS stripes on a '69 Mach 1. Several months after installing them on that car, they started to craze or delaminate or something like that, so he decided he'd never install NOS stripes decals again.
My cars lower left fender got damaged unloading it from a trailer when liberating it from the second shop I had it in. The lower half of the fender had to be repainted, and I lost my 340 Six Pak decal on that side. A friend of mine who also has a T/A had an NOS decal he let me have, and it looked pretty ancient! My local body and paint wizard Dave shook his head when he looked at it, but he carefully installed it with me looking over his shoulder, and it looks great.
Guess I've been lucky, but to your question, I don't think there is a real good way to tell if a decal is "fresh" until you try to install.