@ajlittoz - my sincere thanks for your help.
My document contains commercially sensitive information, so I would not be able to send it, however, I have performed some more tests/ investigations.
I know that the document format is “layered”, and once at the level one can view the file data, the simple file is relatively easy to follow, however, the complex example, unintelligible.
I tried copying an equation from the complex document to the simple document, and was able to add a number to it.
Taking a formula from the simple document and adding it to the complex document did not allow me to add a numbered caption (there is a greyed area where the number should be).
I tried copying the entire complex document to the simple document, and I was unable to add numbered captions to custom captions.
The complex document has figures, tables and drawings - many of which have numbered captions.
If I take an equation in the complex document and add a standard caption, that works, but the custom caption doesn’t!
I am wondering if there is something in the complex document that has “upset” the document - and maybe changed the file format, which is then preventing the custom caption being usable.
If I can deduce if this is a possibility, or can identify the offending item, I will test further.
I was not expecting the file formats to be different between the two documents, hence I am wondering if that is then issue, but I expected Writer would fail if there is corruption in a file.

My thanks for your help.