I think you're on the right track, the query just need a little tweet. The main thing are
1. Convert the integer return from DATEDIFF to string
2. Append + ' Years' string at the end of each condition
CASE
WHEN Users.ResignationDate IS NOT NULL THEN
CONVERT(VARCHAR(3),DATEDIFF(YEAR,WorkStartDate,ResignationDate))+ ' Years'
ELSE
CONVERT(VARCHAR(3),DATEDIFF(YEAR,WorkStartDate,GETDate())) + ' Years'
END as AncinitetViaÅr