This works for me on a Catalina machine and is known to work on Mavericks (HT @bobsmith76 for persevering).
/usr/bin/defaults -currentHost write com.apple.ScreenSaverPhotoChooser 'SelectedFolderPath' "/Users/you/sub/sub/folder"
I used hot-corners to turn on the screen saver, and set different default, then when I enabled screen saver again it used the new folder.
IfNOTE if you need to adjust values inhave System Preferences open when making the dictionary element do likechanges then this may cause the wrong thing to happen (setting name=XX in CustomFolderDictlike the screensaver config flipping to a non-image screensaver - we both ended up on the Message screensaver this way).
/usr/bin/defaults -currentHost write com.apple.ScreenSaverPhotoChooser CustomFolderDict -dict-add name XX