In short, you can’t.
Windows always controls which network connection is used. If you have multiple network connections (both active) to the same network (e.g., 192.168.1.x), then Windows will ALWAYS use the first one listed under Network Connections->Advanced->Advanced Settings->Adapters and Bindings->Connections. The other network connection goes UNUSED. Of course, you can reorder them if you like.
The only way to make Windows use both network connections is indirectly, by placing each on DIFFERENT networks (e.g., 192.168.1.x and 192.168.2.x). If certain resources are only available on one or the other, then obviously Windows MUST choose the appropriate network connection.
That’s the way it works. You can never DIRECTLY control which network connection is used on a per application/service basis. But there is a workaround.
If you install something like
VirtualBox, you can create a guest VM on the host. Now use the first network connection listed in Network Connections->Advanced->Advanced Settings->Adapters and Bindings->Connections for the host, and pass the other network connection to the guest VM for virtualization. Whalla, each environment is using different network connections. And now you segregate/limit your activities by the choice of host or guest VM (i.e., INDIRECTLY).
Of course, you could accomplish the same thing w/ a separate PHYSICAL machine. But the use of a VM makes it more practical. And w/ VirtualBox’s seamless mode, you can do a decent job of producing a seamless transition between the environments.
Not a perfect solution by any means, but it’s the ONLY way to control multiple network connections to the same network. Windows simply doesn’t provide a means to make associations on a per application/service basis.