Reporting on A Sharepoint List with Multiple Person Columns

Hi Redacted_VAR -when we are working with multiple relationships between tables, only one relationship can be active at a time. The active relationship is the default as you are aware. 

Suppose you want to get the FirstName from the User Information List for both the Administrator and Customer columns.

measure for administrator:

Administrator Name =
CALCULATE(
MAX('User Information List'[FirstName]),
USERELATIONSHIP('SharePointList'[Administrator],'User Information List'[ID])
)

another 

Customer Name =
CALCULATE(
MAX('User Information List'[FirstName]),
USERELATIONSHIP('SharePointList'[Customer],'User Information List'[ID])
)

when using these measures in your visual, the context (such as rows or filters) properly reflects the desired relationship.if you see the same result for different categories, it’s likely because the relationship isn’t correctly activated for one of these columns.

Hope it works now, if any share your pbix file with dummy data for further analysis.