We are turning our roof into an unvented roof assembly by raising the roof and blowing in SPF. We are planning to leave the existing vapor barrier down but remove the fiberglass batting and then adding 6" of SPF in all the cavities, to completely seal and insulate the house. Should we have any concerns about doing it "upside down" and not spraying the foam directly to the underside/sheathing of the roof?
The process by which heat energy in the form of light (usually IR unless the substrate is hot enough to glow in the visible range) is emitted more strongly by warm surfaces and absorbed by other materials especially those of low IR reflectivity (think matte black finish). Radiant heat transfer does not require a medium. Foam insulation materials, such as spray foam insulation, are opaque to thermal radiation, like most solid materials. http://m.youtu.be/ggLAUsiuI_o
I have never used foam insulation before and this was easy for me to use right out of the box. I had a 4'x8"x8" cavity in my basement that houses a waterline. When the previous homeowner installed this they put no insulation in at all and being that it's an exterior wall in the basement and I live in the Midwest that thing was pushing so much cold air in it was incredibly uncomfortable. Out of the box and job completed in about 5 minutes. Stopped all drafts and created a nice 2" barrier on the wall in which I will install some extra bat insulation over it. 4 stars because the spray isn't very good passed 6-8" from the surface. Make sure you can reach the surface you want to coat. Great for small jobs!
While coatings may potentially stop minor leaks, the roof should be properly repaired and dried prior to coating application. Coatings may be able to seal pinhole leaks, which are leaks not visible to the naked eye. If the roof is leaking, the roof leak will need to be identified and repaired prior to any recoating; do not expect the coating to find and seal the leaks.
One of the high-tech insulation products being utilized these days is a foam-spray product called "Icynene," which is a foam that starts as two liquid components (a and b, if you will) that are heated up and sent through two hoses and meet at a tip of a gun where the magic begins. This is a thin film that expands to 100 times its volume in eight seconds, when it's permanently set up.
The video below is from a house near Charleston, South Carolina that I visited recently, and you'll see that the homeowner in this case didn't get his money's worth. I knew immediately when I walked into the attic that something was wrong because it was hot up there. In a properly insulated spray foam attic, the temperature won't be much higher than the house temperature. 
This is more common with closed cell foam, but it happens with open cell foam, too. Since closed cell foam has a higher R-value per inch, installers generally spray 2" in walls and 3" in rooflines to meet the energy code requirements of R-13 and R-19, respectively. (I'm not going to dive into the energy code here, but these numbers apply to many climate zones, the latter being allowed under the UA tradeoffs rule. See the Energy Nerd's blog on this topic if you want to argue.) https://youtube.com/v/ggLAUsiuI_o
The insulation at eaves level will leave your loft area comfortable for use and free from condensation. By installing the insulation at rafter level, it keeps the loft void warmer and prevents condensation build-up, which can otherwise occur when increasing insulation at ceiling level. The warmer, drier, cleaner roof space eliminates the risk of pipes and tanks freezing.

During colder months, 2 component foam is very sensitive to temperature variances. Per product instructions, both tank temperatures need to be above 70°F (21°C) for at least 24 hours prior to use. All application surfaces should be clean/dry and above 60°F (16°C) prior to application. Variance outside of the recommended temperature can affect foam yield and performance.

Roof Spray Foam Insulation