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I have created a new table in Data verse from Excel upload, everything else works but the primary column selected is incorrect. I cannot change my primary column, is there a way to change to different column or selecting a primary column before uploading.
Once created the Primary Column is there for good. But do not confuse the Primary Column with a Primary Key, as it is not. Where their is a Lookup field defined that points to that table it is the Primary Column field is what is displayed in that field.
Internally the Primary Key is a system generated GUID that is held in a field with the same name as the Table but with an 'id' suffix. If you need another column to be unique (or is the unique key in another system) you can define an Alternate Key for that column.
Edit: if it is also about importing data into a different column, you can configure the Mappings for data import (note: data import is slightly different depending on where you do it from)
https://learn.microsoft.com/en-us/power-apps/developer/data-platform/import-data
https://learn.microsoft.com/en-us/power-apps/developer/data-platform/create-data-maps-for-import