I was attempting to do the same thing, and found that as of django-south 0.5, south doesn't handle this for you.
Like was stated in the previous comments, you should probably create your south migration first, but then you will have to manually go in and delete the unique index that django initially creates when you do your first syncdb.
use mydb;
desc mytable;
That will show you the schema for the table, and you will see that the field will still have a value of "UNI" in the key column.
SHOW INDEX FROM mytable FROM mydb;
Should be an index that has Non_unique set to 0.
ALTER TABLE mytable DROP INDEX indexname;
If you look at the table schema again, you will see that "UNI" is no longer in the key column.