Well, there is no difference documentation, as there is no difference. Both are same Backup Exec softwares with same features, the only difference that I can remember is that SPN is not supported with Backup Exec 12.x 64 bit. There are no other known limitations in terms of these softwares. It is totally dependent on what kind of architecture you have. So, if you have 64 bit OS, you use BE 64 bit, and if you have 32 bit OS, you go for 32 bit BE.
Please mark it a solution, if this is useful.
Thanks