I think that's the issue: Our transport time difference is pretty small where I do most of my diving. Where the DCS hit happened, it might have been 10 minutes longer to the chamber and while 10 minutes may be the difference between life and death with an MI, the hospital with the chamber is, to be frank, a lot better than the closer one. I'm not sure which would end up treating the patient sooner, even with the added drive time. There are other hospitals en route from that dive site to the chamber as well, if things went south en route. And with anything that involves shortness of breath, I'd be calling emergency services and letting them decide and transport.
At the site I most often have students, the transport time is the same to any ER, including the chamber. (We have "pill hill" in Seattle with multiple hospitals in a small area.) Emergency services, however, has SOP to take the patient to the county hospital/level 1 trauma center, not the one with the chamber. We're also at an advantage in that the chamber can accommodate multiple patients (more than a dozen, I think) and, if pressed, have 3 separate treatment protocols going simultaneously. That's a far cry from the remote location where maybe the chamber operator is awake and sober, or maybe not. Maybe somebody is already in the chamber, or maybe not.
Ultimately, this seems kind of like a situational thing. For most dives in most parts of the world, the closest ER seems like the best bet. I may just live in a weird (blessed?) corner of the world.