The app is too unreliable to trust. It should be plain evident that site of railway is always the first one to check-renfe.com. It is a rather awkward site that needs some thinking or knowledge of how it works. From Vigo down south to PT its Celta-MUST RES and this is CP+Port railways, but apparently with long period of works=bus replaceing. IF you cannot find tain wanted on app-add manually-in ES this will be needed much more as elsewhere.
And-you should also have noted that its simply IMpossible to book only RES/seat in ESpana on RENFE-that should also have been plain obvious to reach -or do you do the walk with the shells? In that case RENFE has a ultra-cheap local pass for Galicia for 3-5 days or so-much cheaper as using a pass.
It might be that we simply have not received the relevant timetables yet. You can double check the timetable on Renfe's website and simply add the journey manually in your pass, should it not be available by the time of travel.
You can't book Spanish reservations online. RENFE made that very difficult with the result that they're difficult to get.
Here are the known ways to book Spanish domestic trains: