In Oblivion, toggling POV was instant. In Skyrim, it's slow and annoying for the sake of being more cinematic. Well, I want functionality, not esoteric aesthetics.

Anyone know of a mod or .ini setting I could use to make the toggle happen instantly?

You can speed up the mouse scroll zoom and the speed of the camera while mounting a horse by editing these lines in your Skyrim.ini under
[Camera]
fMouseWheelZoomSpeed=
f1st3rdSwitchDelay=
iHorseTransitionMillis=
fMouseWheelZoomIncrement=

You can do the same for opening and closing books: fBookOpenTime=

[Camera]
f1st3rdSwitchDelay=0


...I think was the one.

i actually don't have a [Camera] section in my Skyrim.ini, does it matter where I write it in?

Shouldn't.
Edit, to be more clear. You should add a camera section and put that seeing in it.