Probably use something like this
SELECT
SU.Name AS UserName, SR.Name AS RoleName
FROM
sysUsers AS SU
INNER JOIN
sysUsers AS SR ON SU.GID = SR.UID
WHERE
SU.GID <> SU.UID
ORDER BY
RoleName, UserName
Borrowed from SmartBihari's Blog
EDIT 1 To Get the System Roles associated with a user.
The sys.sysmembers is a system view which has the memberuid and the groupuid as the only columns. you can use the user_name() function to retreive the name of each column.
USE [YourDatabase]
SELECT user_name([memberuid]) as [Username], User_Name([groupuid]) as [Role_Name]
FROM [sys].[sysmembers]