arp -a is going to give you the MAC addresses of remote machines, or arp entries for "other" ips. If you want to quicly find out the MAC address of a remote host on your network that you have the IP for, just ping it, then type arp -a and you'll see the IP address you were pinging on the left, and the machines MAC address on the right.
Basically, when two machines are communicating over TCP/IP, they're really just two machines who know the MAC or "hardware" address of the other machine, since that's what the machines really need to figure out in order to talk, regardless of the protocol.