[mysql] How to delete a certain row from mysql table with same column values?

All tables should have a primary key (consisting of a single or multiple columns), duplicate rows doesn't make sense in a relational database. You can limit the number of delete rows using LIMIT though:

DELETE FROM orders WHERE id_users = 1 AND id_product = 2 LIMIT 1

But that just solves your current issue, you should definitely work on the bigger issue by defining primary keys.