The Mono/E position was initially designed to get a DD to run in Pseudo Mono mode. Mono coils were supposed to run in the Normal/DD position on the switch. However, it was found that some users found this confusing, and most users were running their Mono coils in the E/Mono position, so the labeling of this switch changed on the GP3000.
Now in terms of performance, most Mono's won't run better in Mono or E mode, but the threshold can be a touch smoother. If you're trying to run in Mono in difficult ground, but all means try the E/Mono mode.
However, in normal ground, the Normal/double d position on the switch can be a touch brighter. Some people can't hear the difference, but it is only noticeable on the faintest signals.
Now, what I have discovered over the years, is that certain monoloop coils just didn't like the Mono mode, and perform far better in the N/DD position. So it definitely pays to bury a range of targets and have a bit of a play, and see what works best on your machine and coils.
cheers