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I am looking at using a Stonebow with my Bolt Ace in order to deal with DR/Bludgeoning. If I were to shoot Sharpstones from my stonebow, would I encure a lack-of proficiency penalty since sharpstones are exotic ammunition?
There's no such thing as proficiency in ammunition or exotic ammunition. The word 'proficient' in the description of the sharpstone is meaningless.
If they are listed as exotic, I think you would either incur the -4 to hit penalty or be unable use the ammunition to deal slashing or piercing damage (because you don't know how to use it). I'm not sure which it would be.
Honestly either way I would just use regular sling bullets. Either penalty makes them pretty much worthless.
However, Paladin of Baha-who raises a valid point. Generally proficiency is reserved for weapons. Without seeing how the item is presented in the original book its hard to determine what the pword proficient in the sentence is supposed to mean. Generally you don't have proficiency with ammunition.