Do I need to add desired UK counties to edit.front.invoice.xml? (Currently on US, Canada and Australia are there)
You can if you want to, but that file will get replaced when you update CBSubs so be sure to have a backup of your modifications.
Can I import correct counties into the comprofiler_provinces, or will that create issues? (Obviously I will also import correct province_iso_code, country_iso_code2, province_name, province_title
You should be able to as I don't believe CBSubs will override those tables for new rows.