Curious as to why applying material to the roof helps road noise. Does it just dampen resonate frequencies?In my experience, sound proofing the roof and doors pays the biggest dividends in sound reduction for road noise. If its engine noise that is bothering you then obviously a focus on the fire wall / hood is warranted.
As to the roof. . . If you have no sunroof it's usually a fairly easy job and it will really make a difference. If you have the moon roof then its going to be more of a pain but there is still plenty of roof structure to deaden. With the Pano sunroof, I can't see it making much difference (but of course every little bit will help)
As to the doors . . . The RAV's doors really sound and feel undampened. Based on Sunken's experience they are completely untreated from the factory and I would expect a big improvement in road noise reduction. It should also help to reduce many of the rattles and help with mid bass for the sound system.
One hard lesson I learned is that it is best to do this type of work in warmer temps. All the plastic bits and pieces that you are prying off are MUCH more likely to crack / break in colder temps so find a warm garage or wait till warmer temps. The sound deadening sheets will also be much easier to apply in warmer temps.
At least for now, I won't be joining y'all on this project. Our XSE is the wife's daily driver and there is no way she will approve of the disassembly needed for this project on a new vehicle. Have fun!