Click on the field --> Default Properties --> Sort --> Move the not assigned to top
So whenever you uses the field since its default property not assigned will come @top
Hope this helps kindly mark this answer as correct or helpful to close the thread and as well it will be helpful who are looking for the same solution
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Please go through attached workbook. Create a set on dimension Assignment as Not Assigned based on value 'Not Assigned'. Drag it on row shelf before Assignment, right click on it and unselect Show Header option. This will help to show Not Assigned always on top. Also, it will provide flexibility to sort other members of Assignment field in Ascending / Descending or alphabetic order.
Hope it helps you.