Got it to work, although there is a definite knack to it! Pressing the pedal as hard as I could after coming to a stop didn't work for me.
Instead, I brake as normal until the car comes to a stop, then quickly release the brake pedal and then gently press it again.
It's a little hit and miss though, so will take some finessing. The look of confusion from the car behind as my brake lights were flickering on and off.
If you're not quick enough, when you release the brake pedal before pressing it again to activate the hold feature, the car can creep / jerk forward.
The noise the brake pedal makes when doing the second tap is very un-Mercedes-Benz too.
Not quite sure why it needs to be the way it is, on my Skoda Kodiaq you just need to press the brake pedal a little harder after the car comes to a stop to activate 'Auto Hold'. There is also a button to turn the feature off completely if preferred. Seamless.
I'm sure I'll get used to it. Thanks for all the advice.