Ace, thankyou, that's now working as expected. Windows asks Pi-hole and gets a response from Pi-hole. Windows asks an external server and gets a response from that server.
Earlier on Avast's "Real Site" feature was intercepting those requests and sending them to its own DNS server instead, so you had no blocking and the wrong server responding to the tests.
Hopefully now you will see Pi-hole dealing with these. You can watch this in real time in Pi-hole's web admin interface. Go to Query Log then tick Live update.
You can still face issues, where your browser itself is sending queries to its own server instead of the configured server, and then you have to find that option and disable that too. You mentioned Chrome "Secure DNS", so keep an eye on that. You should be seeing everything in Pi-hole as above.