It is a contract by conduct. By entering the private land you are entering into a contract by parking there. The terms of the contract are the signs at the location.
Whether you choose to read the signs or not is not relevant. . . Unless those signs are not prominent, legible or contain unfair terms.
The NtK is PoFA compliant so the keeper can liable for the charge. The only way it could fail PoFA compliance is if the details of the charge are not adequately brought to the notice of the driver. Do you have any pictures of the signs? Can you get some with an overview of the car park?
You have not redacted the VRM or PCN number on your pictures which means anyone with that info can log into the DE website and cause you some pain if they were so inclined.
Have you tried Plan A yet? Contact the landowner/business who contracted DE and asked them to get the PCN cancelled? Plan B has failed, especially with that appeal. Plan C will be a waste of time but you can try an appeal to the IAS.
Plan D will be where you get the best chance to get this cancelled because the only truly independent arbiter is a judge who would decide whether you owe DE a debt.
