As per the wiki, it says that pipewire-pulse.socket 'should' be enabled by default when installing the package, and that no further action should be needed, however I have found this is not the case. Upon rebooting after removing pulseaudio and installing pipewire-pulse in its place, I ended up with zero audio. Likewise, trying to enable the socket manually wasn't working as the service files all seem to be in /usr/lib/systemd/user/ which apparently isn't sourced with the normal "sudo systemd enable <foo>" command. I stumbled across this command on a Fedora bug report, which after reboot seems to have done the trick:

sudo systemctl --global start pipewire-pulse.socket

So now that I've run this, I have sound and it appears that Pipewire is doing its job as the pulseaudio replacement I was wanting.

I'm hoping this is just an oversight and can be resolved during install time though for others.