Hi! I also struggled a bit with it at first. After scanning the QR code the 1st time, the app hanged for a while. I then tried to “go back to the previous menu” (slide from right screen edge towards the left). This prompted me to select whether I wanted a PIN / biometric identification for AGOV. However, somehow, the AGOV website didn't pair with my phone, I had to delete the account association from the AGOV app.
After that, I exited the app, scanned the QR again, and things went smoothly this time.
(Also, for what it's worth, when I first launched the app and paired my phone to the AGOV account, I had the “Secure app spawning” exploit protection disabled, see Settings > Security > Exploit protection).