It's very possible to figure out if brass is once-fired, if you pick it up yourself. You just need to add up all the clues. Most of them show you that brass has been RELOADED, but if you find a pile of consistent brass that lacks all the "has been reloaded clues," then you can be pretty confident it's new. The only problem is that there might be a few random cases mixed in with the same headstamp, left by someone else.
There are only two ways I know of to identify OF brass. They apply only to military brass, and they're still not 100%
1. crimped primer pockets
2. if it's military rifle brass, the annealing will still be clearly visible on the case neck. This will polish away after tumbling.
It would be possible to reload a case without removing the annealing surface oxidation and/or crimp, but unlikely.
To tell a case is not OF is much easier:
1. chamfered case mouth
2. chamfered primer pocket
3. tell tale vertical scratches on the inside or outside of the case mouth/neck
4. headstamps worn
5. rim scratched up in multiple places
6. Big pile of brass left on the ground of the same caliber, but of mixed headstamps like what a reloader would leave.
7. The sizing "ring" visible near the case head.