Much depends on how you intend to use MPLS and what the MPLS vendor can provide for QoS. Much also depends on the features of your equipment.
If you use the MPLS cloud only between two sites, you might be able to implement almost any QoS classes your equipment supports.
If you depend on the MPLS cloud's QoS, you'll likey need to work within the constaints of what the MPLS provider can provide for classes, usually 3 to 6 classes. Often a priority class can be obtained for real-time traffic like your VoIP although often at extra cost.
For ports, Google research should provide the default ports. Note, often default ports can be overriden. Windows "stuff" tends to use the same ports.
Some Cisco equipment also offers NBAR which can identify some applications "better" than just on ACLs (matching ports). For example, later versions of NBAR allows you to "look" at the Citrix type code (e.g. remote screen vs. Citrix printing).
