Well, that was simple, no scripting required. If you're using IPv4 (you can check here https://www.google.co.uk/url?sa=t&rct=j&q=&esrc=s&source=web&cd=2&cad=rja&ved=0CDoQFjAB&url=http%3A%2F%2Fwww.amiusingipv6.com%2F&ei=Bq4_UpakM4vv0gXboIDwCQ&usg=AFQjCNHiUnyKvVcUe8Z966YwoycLI28urw&bvm=bv.52434380,d.d2k)
- Turn Windows features on or off.
- Turn on RIP Listener.
- Disable your internet connection that cannot connect to the website you are trying to access, and 'tracert' to the website: make a note of the IP address of the website, and the first IP address in the hop list ([FIRST IP]).
- Type in 'route print' and make a note of the Interface number of your secondary internet connection.
- Type in 'route add -p [WEBSITE IP ADDRESS] mask 255.255.0.0 [FIRST IP] IF [INTERFACE NUMBER] metric 1'
- Reboot.
All traffic to the website IP address (be it mail, FTP, whatever) will go through the secondary connection, all other traffic goes through the main connection.
IPv6 instructions here: http://windows.microsoft.com/en-gb/windows7/configuring-multiple-gateways-on-a-network
My setup is just an iPhone connected via USB as secondary connection and a Home Hub connected via ethernet as primary.
Hope this is useful to someone else - but of course, no one should ever think of using this to get around IP blocks on message boards...
Sarah