Great question and topic. A huge
energy factor effecting most climates on earth yet is routinely ignored. Reflectance and Emmisivity are the two measurements that are used for ratings.
The cool roof rating council is a great resource for learning the science and some of the specific products that they have tested under lab conditions.
http://coolroofs.org/resources/articles-presentations-and-links
Painted, Bright White Metal seems to be the highest performing cool roof cladding. While the bare and silver products have high reflectance values, their emmisivity lacks far behind the painted products. Another benefit is that white paint seems to better resist UV degradation.
Most research suggests that adding a vented airspace directly below the metal increases performance but its a tricky detail and difficult to make pay off IMO. Choosing bright white metal (with exposed fasteners) is comparable in up-front costs to high-end shingles in our area yet represents a huge jump in durability and energy performance. I feel most metal roofing systems tend to vent a little on their own compared to shingles.