A conditional Yes.
In the design view you can high light the desire field, right click and select primary key option. When you save or eixt and save from the design mode, if all the conidtions are met (unique, no nulls), it will save the table with the new index.
While in table design modem you can also select from the menu, "View" and then "Indexes". Here you can add your required indexes including adding two fields together to act as the primary index, or meet a search criteria. Once again, all the conditions for the index have to be met before you can successfully save.
If you do not have a unique field that allows you to successfully save the design, you do have the ability to create one. First backup your table. When you create a new unique ID field, you have two options.
First when you define it, define it as an "autonumber". When you save the table, you will be warned about integrity rules (because you just defined a field that requires a value when you have 100's or 1,000's of records with a null value.) The system, if successful, will numeric add a sequential value to each record.
Or you can define the field to your specifications, and create some code to update the field for each record.
Once complete, you can make the new field the primary field.
Of course if you create your own unique ID field, you will have to recreate each relation. (Hint: If have relations between tables and have to add a unique field for each table, then you pretty well have to use code to loop through each record and ensure the foreign key matches the new field. Messy)
Richard