no you cannot hotswap domain membership... but there's no technical reason we can't get the machines seeing each other while not on the vpn...
lets start with the basics...
what's the computer name of your home win7 box? lets call it win7 for now
what's the computer name of the xp work laptop? lets call it xpbox for now
what is the inside ip address of the win7 box? lets call it 192.168.1.10 for now
what is the inside ip address of the xp work laptop? lets call it 192.168.1.20 for now
what is the make/model of the network attached hard drive, and ip address?
now, from the xpbox:
start > run > cmd
ping win7
(insert win7 computer name there)
(what happens, do you see an ip address? does it match what you expect it to be? does it reply or say unknown host or time out?)
ping 192.168.1.10
(insert ip of win7 box there) does it reply or not
start > run > \\win7
(insert name of win7 box) what happens?
from the win7 box:
start > run > cmd
ping xpbox
ping 192.168.1.20
start > run > \\xpbox
(substitute where necessary, report what happens from each test)