Your caution / curiosity is well justified. Home guys can pull off a lot of "odd-ball" stuff that makes perfect sense to them, but is not marked at all for a future owner. Casting chamber, as described above, is really good step. So would be slugging the bore. For example, there was a "wildcat" 6.5x57 - so, as I understand, a "normal" 7x57 case, necked down to accept about .264" bullets. So your chamber casting might suggest 7x57 (although the neck should be smaller in the chamber), but a slug through the bore will be a lot closer to groove size .264" than to .284". And, about any combination has likely been tried at one time or another. Military barrels were readily available in many bore sizes - at one time - screwing a 6.5x55 barrel Small Ring Mauser barrel into a rifle originally made for 7x57 has likely happened often, for example.
Ultimately, you will use clues to determine what the unmarked barrel is chambered for, and sooner or later, will have to fire some rounds through it, based on those clues. As mentioned, what "fits" is often not a good clue - variations in design pressures - modern ammo in 100 year old action, etc. Many details of SAAMI cartridge design are to avoid closing potentially dangerous case into a rifle - like 280 Rem into a 270 Win - but home guy, for his own reasons, could ignore all that and "make his own".