Quick summary of issue: I had two near-identical designs of PCB using the CC3235MODASF. The more recent one was giving severe problems starting up correctly on powerup.
Please refer to earlier thread https://e2e.ti.com/support/wireless-connectivity/wi-fi-group/wifi/f/wi-fi-forum/1202094/cc3235modasf-power-up-reset-not-working for massive levels of detail on work carried out.
That thread is now locked, so I can't post the solution with it (if a moderator is able to tack the following text to the end of that case, it would be tidier...)
Now, revisiting the problem, I have at least found a solution, even if I don't really understand it.
I discovered that the device would power up correctly if I had 'scope probes connected to the programming connector Tx and Rx pins. These would provide a slight DC leakage to path (about 10Meg).
I found that adding two 4.7Meg resistors to ground from pins 46 and 47 mean that the SoM now starts up properly.
It is quite bizarre that two PCB layouts, almost identical, in terms of tracking of those two lines behave so differently, but it is absolutely repeatable.