You are trying to add a new Value to a field which already exists in the field.
Alternatively you might be trying to change an existing value into one that is already in the field.
The error message occurs because you have an index on the field to prevent duplicate values being added to the field.
The solution is to inspect the field for the value you intend to add. If the value is already in the field then you message the user indicating that the value is already there, and stop the process of adding the new value.
Tell us about your application, database and table design.
Access is merely warning you of a condition that should not happen n your set up, and preventing it from happening.
We need more info to advise on how to stop it from happening.