is there a way to remove brake callipers for painting?

Yes. Take them off.

Funny, but true.

You don't need to remove them for painting.
 

Just mask everything well enough and use the high-temp paint.

ok, hahaha, what is the procedure?

It's already time-consuming enough to do it when they're on...
 

I would just mask off everything and do it. I would only take them off if I had another set to put on.

two 13 mm bolts on the front calipers.
 

i forget the size of the rears.

you'll need a fairly long breaker bar or a big ass ratchet.

for the fronts, loosen the brake line holding thingy
first - it'll give you room to get to the top bolt.

but like AudiJon said, you don't need to
remove em for painting. it'll prolly be easier
to paint if you don't remove em. just spend
a lot of prep time... cleaning and then masking.

he doesn't have/work on B5 S4's... he doesn't know.
 

but if you look in the tech articles...
or stfa...

Like so:
 

Bonus points for guessing the owner of the garage.

<img src="http://tychl.txf.com/brakebolts.jpg">

That is too easy :p
 

Thanks for the OBDII and when do I get my bonus points!?! :p