I intend to contest the PCN, but in your experience is this worth pursuing, or do councils usually stick rigidly to the letter of the rules in cases like this?
Experience of this forum is that the London councils are venal and rapacious, and Enfield is no exception. They very rarely give way, but notwithstanding this we always recommend putting in some representations. However, just so you know, >95% of all informal challenges to a PCN served at the roadside are rejected. Councils do this, because they know that most people then just cough-up to get the discount. Formal reps against a Notice to Owner, the next stage, are usually looked at in more detail, but the discount option has gone by then.
It is, however, difficult to think of a robust appeal argument in your circumstances as the council have not done anything untoward; a CEO saw your car, it had no parking session, so served a PCN; what else would you expect ?
Maybe in your favour is the convention that time is always allowed in which to pay for parking after having parked, otherwise nobody could ever park legally ! But appeal decisions on this go back to the ticket machine era. What was not allowed, and appeals failed on this, is to go to get change for the machine, and your circumstances seem to fit this sort of scenario. There is no requirement in law for any period of observation, and indeed, for a parking bay requiring mobile phone payment, it is difficult to think why any observation period should be necessary.
Sorry if this isn't what you want to hear, but it is cold reality in London
Anyway, wait a bit for others to comment.