Terry Webbs hi Terry. I can confirm the first screenshot is exactly like my configuration.
About the second one: I don't have an ethernet but a Wifi, anyway I can still manually check the DNS settings in Advanced section and it's "correctly" (for my usage) set to 192.168.1.109 which is my PiHole IP address. The PiHole is also a DHCP. If/when I deactivate NextDNS, the hosts are being resolved by PiHole.
By the way I don't get how the network configuration is related to an app that is supposed to start at boot and it doesn't. Is it clear that I expect the app to open after login (like many other apps do: Docker, pCloud, PIA VPN, etc....) but it doesn't?