As a first step I would speak with the users and try to understand why they add additional items in the outbound delivery. If they have been specifically instructed not to do so, there must be a reason why they keep on adding items manually. Is it the poor quality of the training documentation? Are they trying to correct in their own way some underlying problem that they have not reported to the support team? Business users rarely perform additional activities in the system for the sake of breaking it, especially when it requires more work from their side.
If this is not about a system issue and if this is not because of outdated documentation - usually an e-mail to the supervisor reminding them how important it is to follow the rules does the job.
If trying to persuade the business does not produce the desired results - then I would modify the determination of item categories in deliveries (of course, after making sure that this is not a part of some less known, but important business process variant).
I am not sure what is the specific problem that you face - item category determination is pretty straight-forward. What did you try to do and what errors do you encounter?
One last thing - please make sure that you do not delete by mistake item category determination with certain usages, like CHSP and PACK if these are relevant.
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