It's a pity the keeper didn't do anything about this earlier as they could have tried an appeal to POPLA. Too late to do anything about that now. As far as the debt collector letter, it can be safely ignored. All debt collector demands are to be ignored and no contact with them should be made, at all, under any circumstances.
What has the keeper done about Plan A which is to ask the landowner, presumably the college, to get their agent to cancel the PCN? That is by far the easiest way to del with this and can be dome at any time up to the issuance of county court claim.
The keeper must now wait and see whether CPSM bother to take the keeper to court. Even if they do, there is no guarantee that they will actually let it go as far as a hearing. They could, as in many cases, simply discontinue once they realise that the keeper is not low-hanging fruit on the gullible tree and will not simply capitulate once idle debt collector threats start and are willing to defend any unjust claim.
So, Plan A first. Plans B and C have gone. Plan D, if plan A doesn't work, will be the final one, if/when CPSM decide to actually go to litigation.
For now, please check the CPSM website as though to appeal and see what other evidential photos they have and show us.