Since there is more than 1 meaning for these 2 words, here are the dictionary definitions:
Appoint
1. To select or designate to fill an office or a position: appointed her the chief operating officer of the company.
2. To fix or set by authority or by mutual agreement: will appoint a date for the examination.
3. To furnish; equip: a house that is comfortably appointed.
4. Law To direct the disposition of (property) to a person or persons in exercise of a power granted for this purpose by a preceding deed.
Assign
1. To set apart for a particular purpose; designate: assigned a day for the inspection.
2. To select for a duty or office; appoint: firefighters assigned to the city's industrial park.
3. To give out as a task; allot: assigned homework to the class.
4. To ascribe; attribute: sorted the rocks by assigning them to different categories. See Synonyms at attribute.
5. Law To transfer (property, rights, or interests) from one to another.
6. To place (a person or a military unit) under a specific command.