I'm mostly a Hertz guy - 15-20 rentals per year - with maybe 5-7 per year with National. The reasons I do those 5-7 with National are because they are flat-out better than Hertz at that particular location.
I'm talking about places where National's process, systems, staffing, and/or location is such that an Emerald Aisle rental will always get me on the road faster than a #1 Club Gold rental - period. Focus is 100% on efficiency here, so I don't want to get into car selection, etc. as long as the system works (e.g., the Aisle isn't empty

).
Here are my initial takes, along with the percentage of time a National rental would beat a Hertz rental to the road.
MCO - 100% National is in-terminal, Hertz requires a bus out to Semoran Avenue. End of story.
TPA - 90%, at least as of '05. National has a functioning Aisle, Hertz requires me to talk to somebody to get my keys. 90% of the time, this takes longer than jumping into the first car on the Aisle.
SEA - 80%. Hertz is completely dysfunctional in Seattle. They have an in-terminal location with a large #1 Club Gold area, but it rarely works right. As of last month, I've switched to Emerald Aisle in the Emerald City.
What others are on your list?