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Personally, the only item I ever Poach is Demon Feather, and that only if I have two Black Mages that want Cloud Staff. Everything else I just find more convenient to drop or steal, but it depends on what you want to make I suppose.
A good skill to combo with Poach is Sight Unseeing. To enable it, you can either cast Blind on yourself manually, or equip a Goggle Mask (buy at Mosphoran Highwaste shope, after Stilshrine).
Monographs. Getting the proper Monograph will generally make the rare poach a flat drop from regular kills, at worst at the 5% rare poach chance. You just need about 150k gil to get them all, and the patience to talk to every shop owner in Rabanastre (or any of the other hub towns) a couple dozen times. And check the hunt board a couple dozen times, too.
For demons feather i loot/steal it from gakimaseras in the garamsythe waterway since this is the only way to get it early and make the ivory staff+ the cloud staff availabe as soon as possible at the bazaar.
Stardusts can take some time to get (even more time consuming by poaching than simply drop with monograph) but serpent fangs are not that difficult as there are plenty of snakes in the fey woods.
Oops sorry, thought you were talking about snakes eyes.
Still, you can kill a lot of snakes in the mosphoran higroads where there are 3 humbabas and the condors. With the monograph it's not that long.