Windows version of vCenter you should be able to do that no problem. You just have to set the static routes. I have no idea if you can do that on the appliance.
Take in mind that multi-homed vCenter is not recommended, take a look at this KB article: VMware KB: Verifying the VMware vCenter Server Managed IP Address
When vCenter Server is multi-homed, verify the internal IP (that is reachable by the ESX/ESXi hosts) is set as the management IP; a multi-homed environment is not recommended for vCenter Server. When changing theManaged IP Address from vCenter, you do not need to restart the ESX/ESXi management agents.
Instead of using multiple NIC, why not configure your external network device to redirect traffic to the internal IP of your vCenter ?