I'm struggling with this too. I only just realized that iBooks on iOS apparently uses the iCloud account, rather than the store account, or at least it is supposed to. I get weird, confusing dialogs though when I fire up iOS iBooks.
The Mavericks version does something similar, and asks if I want to change the account I sync with when I log out of one and into another, but it isn't clear what happens if I choose not to.
One thing is clear though, bookmarks and collections aren't getting synced in the way I'd like.