Hi Shadow:
Please tell me you backed up the database somewhere! - You are not completely out of luck if not, but it might make it easier and more complete. Also are you using Picasa 3.9?? If not, don't change yet, but if so it is probably better.
I have never been able to edit the folder names in the database because they are not text files. and the structure is murky. Also when I talk about Pictures I just mean the Picture folders with the pictures and the ini files. When I say Database I mean the files in the Google\Picasa2, and Google\Picasa2Albums folders.
Ok, I am not completely sure about Picasa 3.8 without doing a lot of checking, but in 3.9, the Captions are stored in the tags inside the picture, so you should be able to get the captions back.
The facetags, or at lease an alphanumeric string representing the face is stored in the .ini file in each picture directory, and these strings are referenced to person names in the contacts.xml file, so the main thing is getting all this data referenced to the pictures and back into the database.
The easiest thing would be if you have a complete backup of the pictures folders and database files. In that case you could copy all the pictures back exactly where they were, and copy the database back where it was.
I assume you don't have the above? Otherwise we wouldn't be talking!
I also assume the nas is mapped to a drive letter, if not, do it now.
The next best thing is if when you copied the picture folders you copied the whole folders so the .ini files are still in them. At this point you should put the pictures where you want them to end up, Probably on your NAS drive, and Photos/(folder)\subfolders should be fine. (If that means all the Photos are in photos\ and nothing else is. It is always easier to define the folders to watch if there is a containing folder for all of them.
Use PicasaStarter to make a database somewhere, and copy the least screwed up database there.
Start Picasa with that database, then immediately go to tools-folder manager and set all the directories to remove from Picasa.
Then set the NAS Photos directory with it's picture folders to scan always.
Go away for a few hours until Picasa is done rebuilding the database. It has to rebuild ans scan faces, and that could take a long while. You won't know how well it went until it is done, because the faces have to be scanned, but once they are, they should be named.
See how well that goes before we start trying to do more. You will probably have groups of faces that are grouped together but unnamed.
Good Luck,
Earl