I've read somewhere that some NPC's are less likely to catch you - and so may offer training. Major Gari was my first successful pick-pocket and he is still the easiest, but he has crappy stuff.
Next was Antone, then Anna and He'Li. Never tried Burz. Crock always catches me, as does Braffit. Braffit won't go hostile, just gives you a lecture about stealing from the clergy - Crock, of course, starts a fight that he can't finish. Only tried Barlone once - bad result. Fuzfass and Madras are OK, because when they catch me, they just go neutral and don't start a fight like the others.
So, it seems that the way to train is to steal from the vendors. I prefer to shop-lift because you get to choose the item, which is great for spell books. I tried to shop-lift the special item that Barlone gets for the group, but no such luck.
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