Answer
Mark that specific field as an Alternate Key rather than trying to change the LU's actual primary key — with an Alternate Key defined, users are blocked from saving a new record whose value on that field duplicates an existing row's value, giving you the uniqueness enforcement you're after. Separately, note that a Custom LU's underlying table always keeps ROWKEY as its genuine database primary key internally regardless of any Alternate Key you add — that ROWKEY-based primary key should never be removed or changed at the database level, even from custom database code, when adding an Alternate Key purely for business-level uniqueness.