Not sure about VMM specifically (edit: do you just mean virt-manager?) but when I was figuring out how to use libvirt, the key turned out to be to add -c qemu:///system to virsh commands and such. I’ve written a more detailed guide here in case that’s helpful.
$ virsh -c qemu:///system net-start default
error: Faailed to start network default
error: internal error: Network is already in use by interface enp1s0
Running virsh -c qemu:///system net-start default on a host NixOS environment works.
Running virsh -c qemu:///system net-start default on a a NixOS environment that itself runs in a VMM fails.
That is because the default network in libvirt (and thus, virt-manager) is 192.168.122.x/24. In the guest OS, it is already your primary network, so it cannot be used (error: internal error: Network is already in use by interface enp1s0). One way to change it would be to edit connection details, remove the default network and create a new one with different IPs. If you want to have something declarative, I’m affraid there is not much network related settings in configuration, but you can create new xml in /etc/libvirt/networks/ and use systemd service to replace default network.