Yes to first question, no to second one
The pumpout hose would indeed be the first to permeate...but it's unlikely that it would be only permeated hose because a) few people flush long enough clear all the waste out of the head discharge hose and also rinse behind the flush..so waste sits in it too...and b) all hoses except the vent line are anaerobic inside, so ANY bacteria in the head discharge hose will multiply and produce noxious gasses. Which is why it's so important to use the most odor permeation resistant hose. However, a blocked vent would pressurize the tank, causing far more serious problems than just odor--increasing backpressure while pumping the toilet, an eruption in the toilet or out the deck pumpout fitting when the cap was removed, an inability to pumpout because the pump would pull a vacuum...or even a cracked tank. It would be impossible to live with a blocked tank vent long enough for it be a source of odor in the boat.