Have you saved the number on the phone or the SIM?
SIM contacts only allow one number per contact (phone software may hide this from the user by showing multiple contacts as one, but SIM contacts fundamentally consist of one name + one number, nothing more). So if it is stored on the SIM it may well not allow you to add another number.
If it's stored on the phone, either as a phone-only contact or linked to an account (Google, Samsung, Outlook, whatever), then @Dannydet's post above has the answer. If it's stored on the SIM, import it to the phone and then edit it.
Did you try using a different app for contacts? Is a bit strange because most default contact apps in modern phones allow you to add multiple numbers in the same contact.
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