My friend in Germany is using a VPN set the US (not sure it matters) and when he clicks on the link in the invite email that is sent he get this message:
He’s the only one who has had issues, any ideas?
Might well be an issue with the VPN – not sure though.
If they have a Plex account of their own, they should see the pending invite in their account section (Settings > Account > Users & Sharing). There they can also accept the invite.
Otherwise… let them create their own Plex account first. If they use the same e-mail address to which you sent the invite, they should see it the same way as described above. Otherwise you might need to re-invite their account.