I finally had a chance to play around with this and get it working. Thanks AZSlow for the mute on the mains tip, as that DOES work.
For those interested in doing something similar, here's what the configuration is:
1. Set your Master bus to have two sends, one to the headphone out and one to the monirot out (or multiple monitors or whatever). In the case of the Echo Layla, this is Out 1/2 (headphones) and Out 3/4 (monitors) - I still have 5/6 and 7/8 available for other things.
2. Make sure that both of these sends are on and at the standard 0db level.
3. Go to your console view and turn on the Main Outs in the view options - they should be to the right of the Bus displays.
4. Go to each of the Mute buttons on each main out and right click and select Remote Control. Then choose what will toggle the control. In my case, I selected Note C0 since that will never naturally occur in anything I'm doing.
5. Select the buttons so that one of the pairs is muted and the other one isn't. This will make them alternate when the toggle is used (so the headphones mute is engaged while the monitor one is not).
6. Now, on the keyboard (a PCR800), I go to the ACT settings and select a button to disable it from being an ACT button - in this case, I've chosen the A8 button.
7. I then edit the button from the control panel on the keyboard itself to send midi note C0 (you could do this from the control program as well, I suppose, but for one button, it's like 10 key presses).
Now I can use this one button as a toggle for the headphones and monitors. It probably doesn't seem like much, but this is a real pain to do otherwise when you are going back and forth between the two settings. It also functions more or less like some of the monitor switching devices out there that you have to BUY :)
I doubt that this will help anyone much since there hasn't been a whole lot of activity on the post, but maybe it will help someone along the way!