A bit of an update, I sent my Pi back under RMA but the good folk couldn’t duplicate the problem after a week of trying and sent my Pi back to me, but it still played up on me sadly.
I did some more testing to o see if I could isolate the problem:
I moved the PSU to a different power point in case there was something weird with the one I was using. - No Change. I disconnected the mouse, the ethernet cable and the monitor so only the PSU was connected. - No Change
I had some more communication with the folk at Core Electronics and they came up with some theories for me to try, which consisted of doing a full upgrade of my OS and eeprom. It turned out my system was fully upto date as was the eeprom (No Change)
They had me update the keyboard firmware and reset the keyboard configuration in case keyboard mapping had somehow screwed up my keyboard mapping, as follows:
sudo rpi-keyboard-fw-update
sudo apt install rpi-keyboard-config
reboot
rpi-keyboard-config info
After I did the keyboard firmware, I also pulled the keycap on the power button using the provided puller as the power button seemed to feel a bit “different:” to me than the other keys and had a look, cleaned up around the switch (not that there was anything to clean) and refitted the keycap.
After the keyboard firmware update/reset and fiddling around with the keycap, I noted that when turning off the Pi I now got a flash of white when the power button went from green to red when the Pi powered down, and now the Pi reliably turns on on a single press of the power button.
Early days yet, but hopefully the issue is resolved, I’ll let you guys know if things change 
I’d like to thank the staff at Core Electronics, in particular Jane for the patience shown and helping me to resolve the problem, great service!