For the first part of the question; yes, if you by either the collectors edition in store or the digital collectors edition on steam there is a code you enter to bind it to your account.
As for the second question, as far as I can tell, if you bought a Hero & then buy a character pack then you just payed for a hero twice. There are no refund, no discounts, partial refund, not even a free skin or some sort...you juts paid for a Hero twice with out any bonuses or pluses. Unless they are changing this policy, which I hope they do, it's one of the main reasons I'm not buying anything until that issue has been dealt with.
Cheers!
-BBB >^.=.^<