Role Assignment: This can be done using SU01 (by administrator access) if a single or two three users needs to be assigned specific access (roles). In case if you want to assign single access to multiple users you can use PFCG and go to user menu for the access (role) in edit mode which you want to assign. You can as many as users there as per your requirement. The other way of assigning roles to user is via Virsa tool (VRAT). Execute VRAT tool and than try checking SOD (Segregation of Duties) for the role if there is no SOD you can use the tool to assign the access. This is a faster and more controlled way to assign the access. But using tool you can assign SOD violating access and for that
you need to choose either SU01 or PFCG.
Role Deletion: This can be done via SU01 or PFCG. In SU01 you need to login via administrator access and deleted the required access/role. In PFCG you just need to remove the user ID from which you need to remove access.
In both the above cased you need to to user mater comparison if you are using PFCG or running of PFCG Time dependency Job.
Creating New Profile for New User/Old User: This can be done using PFCG.