suppose that he (the seminarian) wishes to pursue an additional degree in something, such as either Liturgical Studies or Canon Law? Is he able to do this, and if so, under what circumstances?
Basically, in the circumstance that his bishop wants him to.
The bishop is under no obligation to pay for further studies beyond those required unless it is advantageous to the diocese to do so. During discernment with a diocese, a candidate may state that it is their hope to study e.g. canon law, but then a bishop may easily say, well, I’ve already got five canon lawyers under my authority, and I don’t need another.
There is nothing wrong with a candidate expressing an interest or acknowledging a personal strength that their bishop may wish to make use of, but no bishop can be dictated to with regard to further studies, and many may have neither the budget nor the inclination to pay for a degree that is of limited use to them. Although many seminarians do specialist studies, it is probably accurate to say that most, or at least large numbers, do not.
This is something to discuss during discernment but as in so many other respects, approaching church authority with a shopping list of requirements - however politely expressed or genuinely meant - is typically not a good idea.

Obviously enough, the fundamental vocation is towards ordination, and everything else is just details. If there is a strong sense of call to a particular academic discipline, it may be advisable to discern a religious community or priestly society that specialises in that area, but even then, there are no guarantees that the path to be undertaken can be arranged in advance.
Cliché though it is, it has to be accepted that if we offer ourselves to the church, we lose a great deal of self-determination, and can’t place conditions upon the offer of self. I’m sure you realise this, but that difficult reality has to be owned and lived, not just acknowledged.
Hope this helps.
In Christ,
Withburga