In fairness to GWR, they seem to use their stock fairly prudently.
As has been said elsewhere on the forum many times, 158s are kept away from the Bristol and Bath area on Cardiff-Portsmouth services at peak times because their end doors mean they take too long to load and unload. The services they are booked for mean they only pass through Bristol and Bath off-peak if all goes to plan. I don't care for 166s - although improving the seating and replacing the defective air con with the same air cooling as the 165s would work wonders - but at peak time it's a matter of getting people on and off quickly enough to keep to time, and the wide 1/3 - 2/3 doors are crucial. GWR simply don't have enough 158s to run 5 car services in any case. Gloucester - Weymouth services are likely the same.
IME most Exmouth - Paignton services are run by 2 x 150 or 1 x 166. There are 158s but they're normally doubled up with 150s. Exmouth - Paignton has a very high turnover of passengers all along the route so again wide doors are essential. When 158s on their own appear, they're normally poor timekeepers due to the dwell time at stations being increased while everyone gets on and off.
Castle HSTs are concentrated on the lines between Cardiff and Penzance where their top speed can be utilised north of Newton Abbot. I don't think they're cleared to work over electrified lines, particularly if they have long swing link bogies, so Weymouth and Portsmouth are out.
158s are best suited to limited stop services where most people are travelling end-to-end. GWR don't have many routes like that, but Exeter - Barnstaple is one - few people board or disembark between Exeter and Barnstaple. True they can't reach their design speed of 90mph, but they can't reach it anywhere south of Bath on Cardiff - Portsmouth services anyway (although 85mph is permitted most of the way between Salisbury and Southampton).
The only places Barnstaple services are guaranteed to stop anyway is Crediton and Eggesford - every other station is a halt. Most services seem to call at Umberleigh IME but every other station is regularly skipped.
AIUI GWR are under pressure to start retiring the Castle HSTs as soon as there's enough other DMU stock to do so - the Castles are very expensive to run. This may well mean that 158s take over their current workings and 165s/166s take over the Barnstaple branch.