I think you are reffering to promoted properties in a document library. These are promoted from a form when it is saved. I am not sure you can modify them but even if you did they would be out of sync with the form itself. Typically you would update the form, publish, and promoted properties would be updated too. Could maybe update XML as well but then you might as well submit it and have the promoted properties updated automatically with the builtin functionality. It goes XML to Promoted Properties, not the other way around.
If you want to update list items there are several blogs and posts on how to do that with a CAML.