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Just buy what you need and break down ammo you already have if you want to make variations of it.
You get cases (not for all ammo types though) by firing your gun, i.e firing a standard .357 has a 30% chance to net a case (more with the hand loader perk).
That's the basic procedure. As you noticed, with .50 cal you're out of luck.
In OWB, I shoot Lobotomites with (plentyful) .357 or .44 and whack scorpions with the proton. inversal axe, melee skill doesnt matter that much for this weapon, though having super slam helps alot. Hopefully you didn't make the mistake of going to OWB at level 40+
The Sink vendor can stock primer and gunpowder boxes, although it can be pretty random sometimes.