Hello Paul , thanks for coming back. My scale factor is set to 100% and I changed my Advanced settings to match yours above but not much has changed.
I think the issue has to do with monitor resolution because I have just hooked up my laptop to two monitors with different resolutions as shown in the screenshot below:

Screen 1 (my laptop) is 1920 x 1200 and the other two screens (2 & 3) are 1680 x 1050 and 1920 x 1080 respectively.
I have just tried setting each one of these in turn to be used as the display, and the only time, without fail, that the Main View URL works is when set to Screen 3 (1920 x 1080). When the other screens with the "odd" resolutions are used, the URL just displays the desktop. I am guessing the OpenLP Main View endpoint isn't able to handle these "odd" resolutions and it would be interesting to get a developer's take on this rather interesting behaviour.