Do you have a wireless router? Or at least both connected to a router at home for internet? If so, then you can transfer over the network too. I imagine it would be faster than bluetooth.
I don't see how it wouldn't work, I just have never tried with bluetooth. I don't currently own 2 macs, or even 2 computers with bluetooth.
I imagine if it did work, it shouldn't be difficult. Turn one mac's bluetooth on, make it "discoverable", then try to find it with the other mac.