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Weird problem - I ve set the phones assign in the console to main out. It works fine for everything on my headphones except for windows media player and other media players. I have no speakers here so I can just listen on headphones. I can see the signal on the front of the motu coming out the main stereo pair but nothing in the headphones.
Converslet DAWs and DJing software caan also be seen coming out the main stereo pair and I can also hear audio through the headphones - any suggestions ?

I don't know for sure if this is your problem OP but it is consistent with the evidence and a peculiarity of Cuemix that might also confuse others.

With nothing else running and in the OP's exact situation.

Start the MOTU Audio Console.
Change the 'Main Out Assign' from the default 'Analog 1-2' to 'Main Out 1-2'.
Close the MOTU Audio Console.

Open Windows audio Playback Devices.
Navigate to MOTU Main Out 1-2. Check the device is working and set it to be the default from the existing MOTU analog 1-2.

That should now work as you expect.

There are two little oddities at play here.

1. Most Pro Audio software defaults to assigning Main Outs to MOTU main outs 1-2. Most Windows audio apps default to assigning stereo outs to MOTU Analog 1-2. This is normally fine because the MOTU then defaults to duplicating the analog 1-2 output on the Main Outs.

2. For reasons best known to itself the MOTU Phones assign ONLY monitors the output specifically assigned to the particular output pair. i.e. Not the one(s) rerouted. That would be double monitoring.

Got that? No? Never mind. Just mess with it a bit and all will become clear.