I don't know if there is a spare unit (and traincrew) available during the afternoon either. I don't think there is at the moment, it's very rare to see anything stabled at Swansea or Carmarthen, when there is it's normally awaiting attention or being used to strengthen particular services. As to train crew, the dark arts of diagramming are a bit of a mystery to me, and I am not familiar enough with the various rostering agreements that exist to even begin to guess whether we could squeeze another trip in without requring additional on train staff.
The first two train into Fishguard are pretty useless for journeys from Carmarthen and the east, but they are there for the reverse flow, allowing residents of the area to reach Cardiff before 0900, and connect for longer journeys. This is crucial to avoid the mistakes of the Whitby line, where the timings are pretty useless for most journeys beyond Middlesbrough. Similarly, the late train back exists to provide connections from further afield to Fishguard, rather than a useful service from Fishguard.
The stabling idea is a non starter. ATW would have to buy or lease a van/car for two journeys a day. Unless a third member of staff can be found to drive it down, back again and repeat the whole thing again at night. It just isn't going to happen!