Breja: The motivation is - if it runs on modern systems already and not through ScummVM, why bother making it run through ScummVM?
Other reasons, besides the ones others already mentioned:
ScummVM can fix all sorts of glitches present in the release or final versions of games, including game logic errors that may have caused unintended dead ends and stuff. I haven't used ScummVM all that much but I think on the website I found a few notes about a few fixed glitches.
Edit: I just remembered, I actually read on the GOG forums that a notorious game breaking bug in the first chapter of I Have No Mouth And I Must Scream was fixed in ScummVM, to name an example.
Secondly, GOG only makes sure that the games run, not necessarily that they run perfectly. There may be performance or rendering issues left in a GOG release that ScummVM most definitely will take care of.
Finally ScummVM can improve games in a number of ways. From what I recall there were some optional interface improvements in a number of titles, I think I saw something like that in Space Quest IV. And I believe ResidualVM (a sister project aimed at 3D games) added an experimental point & click interface to Grim Fandango.