Hi All,
It seems that I didn't check input power properly enough and in short, I was being stupid.
Basically for anyone reading this, I wasn't supplying enough voltage to the 5V input of the ESP DEV board, which meant it was dropping out when initialising the ESP_NOW_INIT.
Explanation:
Although described as a low drop out regulator, the onboard AMS1117 3.3V regulator requires 4.8V of input or higher when more current is being used. Although I was supplying 5v, this wasn't enough when the ESP_NOW_INIT started and it caused the DEV board to reboot. Applying voltage higher than 6V solved the problem.
Please see:
http://www.advanced-monolithic.com/pdf/ds1117.pdf
Please bear in mind that I had other circuitry being powered, including the 3.3V rail to the Class D Amplifier.