Well, they present every single cue in the library in order of recording, not in any episodic order.
My impression of The Prisoner
's music, just from listening to it, is that it was all basically library music, with nothing actually written for a specific scene in a specific episode. So I don't think there actually would be an episodic order.
Well, that's not entirely true. While they did use a great many cues from the Chappell Music Library (more so as the series progressed), around eight episodes did have scores specially written for them, but like so many other shows of the day, they were recycled endlessly. The pilot, Arrival, had a score written for it, but it was rejected. Another score was written and used with some of the rejected score plugged in as well as Chappell Library music. The upshot is that, even out of order, none of these cues were arranged or presented as an "album listening experience." It is little more than a music archive. Once I took task of rearranging them at home, it became easier to sit through. And once I got the rest of the library cues, it became a very interesting listening experience. But until I did that - total chore.