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Well, I can't tell you why it means cookie instead of cake, but teI way I remember it might help you. It's a little weird, so I hope it doesn't confuse you more. Biscoito sounds like biscuit, a biscuit is kind of like a scone, which is kind of like a big, hard cookie. Hope this helps.:-)
Shouldn't this be "Um biscoito com chocolate"?
In a different one, we are told that it's "leite com chocolate" because it's milk with some type of chocolate in it, as opposed to "leite de chocolate", which would be milk that is somehow not milk and instead chocolate.
So by the same token, "Um biscoito de chocolate" implies that the biscuit/cookie (which isn't chocolate by default) is made out of chocolate. In that case, it wouldn't be a biscuit/cookie. It would be a chocolate, and at the very most a biscuit/cookie shaped chocolate.