By definition you cannot have multiple primary keys.
You can have a primary key that is composed of multiple fields.
You can have additional indexes that are composed of either a single field
or multiple fields.
To view/change index definitions for a table the easiest way is to open
the table in design view and then select View->Indexes from the main menu
and define any additional indexes you want.
You can have a maximum of 32 indexes for a single table; you can have a
maximum of 10 fields per index.