Unless you've used fiberglass before, it may be tricky to pick up first time (are you talking about raw fiberglass
and bottles of epoxy?). You'd need to make a mold first. For many development boards, we used to just use
cut perspex to the size of the PCB, to shield the top and bottom, (it doesn't protect the sides) and use hex spacers
with screws to make the PCB sandwich.
I think many people do this approach for development boards, it is quite common.
If you really do need the sides protected, and really do need a custom sized box, then
maybe sides of perspex could be glued to the top and bottom perspex (maybe using modelers [toy aeroplane]
cement type adhesive? - I've never tried it), or you can get very tiny threaded screws that would be thinner
than the thickness of the perspex, if you can tap a thread into it successfully without cracking it.
A nicer plastic is Delrin if you have access to a machine shop. Then, it's possible to create any shape enclosure since
delrin is available in extremely thick chunks. Of course, then you need access to a machine and an expert.
Another approach (full of ideas today) could be a metal enclosure if you can cut (say) brass or aluminium sheet.
Maybe it can be brazed (I only ever did this once a very long time ago, and I don't know which metals can be
brazed, or how tidy it would be possible. Of course there is laser cutting but it's too expensive to be worth it
(I've done it a couple of times - not for a case). You get a extremely nice edge finish on acrylic sheet with a laser.