You need to identify the gateway address to your VPN, then add a route to route traffic for your destination to that gateway. It's not too complicated if you understand basic TCP/IP routing:
A routing table dictates where all packets go when they leave a system—...
if you can use Linux in vmware or something you can use proxychains easily to satisfy your needs.
We don't have many articles on how to use proxy chains on windows, but hey.. windows have ubuntu terminals now, you can use Linux subsystem for windows and then you can use proxychains.
This might not be the most optimal solution, but this can be done.