I am unaware of a specific ruling in the books (which isn't to say that there isn't one, only that I'm unaware of it). But this comes up in idle conversation in my group from time to time, mainly because we have a wizard that loves to toss out Web spells and we've been fighting a lot of giant spiders lately.
Our take on it is the Web spell is magic, and so it works as written on giant spiders, normal sized spiders, and large groups of normal sized spiders, even those that can negoiate webs with ease. That said, as a player, if I cast a Web spell at a giant spider (or a bunch of little ones) and it ran right over or through it, I wouldn't complain about it. That's a justifiable ruling, even if it isn't RAW.