if both the nic's are reporting 100mbs connection, my first guess would be that it's possibly software causing the transfer to be limited to 5mbs.
If the op is using a third party firewall it might be worth trying an exception for traffic in the local IP range (that used on the home network, or even just the IP of the other computer), so the firewall isn't inspecting the traffic.
It might also be worth trying a different network adapter in one of the machines if the op has one spare (or if one of his machines has two built in nic's).
Going back a couple of years I found the then current version of ZoneAlarm killed my internet download speed (tracked down after much faffing around, and by using an almost identical system without ZA installed to test the speed), likewise I've found odd issues with certain NIC drivers when transferring data on a home network between different versions of windows (for some reason at one point my BIL's network was imposing about a 20% cap per connection when one of his machines running 98SE was transferring to an XP machine, something that had me stuck for ages until I tried a different brand of NIC).
Neither of which will increase the speed massively, but may help get a transfer that is closer to the theoretical limit of 12MB/s with 100mbs gear, if it is a nic driver or firewall issue