I have checked with Rome2Rio and there does not seem to be an easy route from Porto to Baiona, Spain. There was an older post on this site mentioning ALSA bus service in northern Portugal but the website does not seem to have schedules posted from Portugal. Omio.ie lists some bus routes. Any help in finding public transit by rail or bus would be appreciated. Hiring a car and driver is very expensive.
It looks like there's regular bus service to Baiona from Vigo, which you can get to by train from Porto.
Put Vigo as your first destination, then Vigo to Baiona and see if that works for you.
Just a heads-up that Vigo isn't one of Spain's most interesting places. I'd try to choose a different overnight stop if I needed one due to the transportation schedules.