If the two choices were pull case air over the rad and exhaust to the outside or pull room air over the rad and exhaust to the inside of the case -
I would tend to pick outside air over the rad since the CPU's temperature is more important than the case temp (and if the rad were at the top of the case and you had an exhaust fan at the back of the case, it would have minimal heating affect on the lower part of the case where everything else is).
However, if you aren't pushing your CPU much in the OC department and have the rad at the top of the case, then I would say go the other way, since the case air isn't usually that much higher than ambient.
But - I prefer to have both intake and exhaust from/to the outside
If you put the spacer/shroud for the fan above the rad with it at the top of the case, then you could still have the res/air trap above the rad by mounting the res/air trap directly against the top of the case with the bleed/fill tube extending either up through the top of the case or out the back and up.