Thanks for the help chewitt.
I've been banging around it a bit further and have (eventually) realised that it's actually a permissions issue.
I reinstalled Dietpi (as that was the last place I had it working) but then ran in to the same problem. After going around it a few more times I got the hint that there were issues around permissions in the messages I was getting (and I'd set up as root) when I switched to loading Kodi as the user account the VPN addon works again.
I'd like to go back to using libreelec - is there a way to make sure I'm running with user rather than root privileges?
EDIT: Sorry I should have done more reading: https://wiki.libreelec.tv/installation/security 'Single Root User'
so, instead, I need to work out what permissions to set which folders to in order to make OpenVPN happy.