I've only used Caddy as a reverse proxy in production, but on my development machine I use Caddy with php-fpm. That makes me a bit unsure if I understand your questions correctly.
It looks like your Docker (?) image is exposing the php-fmp socket? I did not even know that was possible, but I don't doubt it is.
Caddy has no issues serving multiple hosts from the same server, it can even be with different php-fpm sockets. Caddy will just nod at you, maybe silently question your choice of still running PHP 7.4, but it accepts it and runs. Just make another block with a different host in the same Caddyfile, and it will work just fine.
I use Caddy in production with a PHP-FPM WordPress Docker container in the same way as you describe. I have the site root mounted as a volume on to Caddy container at /var/www/html and mounted in the WordPress PHP-FPM container under a separate path. In my Caddyfile I use the root directive as you've shown but then override it under the php_fastcgi directive to match the path in the WordPress container.
then, i had to take care of permissions, because even if caddy is run as root, php-fpm is run as www-data , so the directory ownership need to be assigned to that