Adding totals based on titles

You seem to have been on the right track, I didn't really need to do anything different than you did.

Here are my results based on your sample data

Total Active Accounts:

SUM(
  (CASE 
  WHEN `PS Variable Stub` = 'TOTALADaccounts' OR `PS Variable Stub` = 'totalO365accounts' THEN `UPN: User Count`

  ELSE 0
  END)
  )

No MFA:

SUM(
  (CASE 
  WHEN `PS Variable Stub` = 'EnabledInMFAExclude' OR `PS Variable Stub` = 'O365MFANotOnAccountRequired' OR `PS Variable Stub` = 'O365MFAExclude' OR `PS Variable Stub` = 'O365MFANotOnAccountRequired' THEN `UPN: User Count`

  ELSE 0
  END)
  )

Internet Blocked Accounts:

SUM(
  (CASE 
  WHEN `PS Variable Stub` = 'TOTALADaccounts' OR `PS Variable Stub` = 'totalO365accounts' THEN `UPN: User Count`

  ELSE 0
  END)
  )

  -

  SUM(
  (CASE 
  WHEN `PS Variable Stub` = 'EnabledInMFAExclude' OR `PS Variable Stub` = 'O365MFANotOnAccountRequired' OR `PS Variable Stub` = 'O365MFAExclude' OR `PS Variable Stub` = 'O365MFANotOnAccountRequired' THEN `UPN: User Count`

  ELSE 0
  END)
  )

  -

  SUM(
    (CASE 
    WHEN `PS Variable Stub` = 'EnabledWithMFA' THEN `UPN: User Count`
     ELSE 0
    END)
   )