Methanol is mainly used to solubilize coomassie blue and to keep the gel from swelling. Acetic acid is used to fix the protein in the gel. one reason it is used is because it is mostly reversible.
The function of methanol is to prevent the gel from swelling, precipitate the proteins in the gel in acidic condition and solubilize the dye in commassie solution, acetic acid is to facilitate the precipitation of and fix the protein in the gel.
Acetic acid in the destaining solution is useful to fix the protein whereas methanol removes unbound dye and thereby reduces the background. We use 25% methanol in the destaining solution and at that percentage methanol doesn't shrink the gel.