A family of Microsoft relational database management systems designed for ease of use.
Why do you need the additional combo box at all? You can simply allow additions in the subform, and select a product in the empty bottom row in the subform when you want to add a further product to the order.
You might like to take a look at DatabaseBasics.zip in my public databases folder at:
https://onedrive.live.com/?cid=44CC60D7FEA42912&id=44CC60D7FEA42912!169
In the section on 'entering data via a form/subforms' in this little demo file, the third form in this section is a simple orders form/subform set up in this way.
If you do use a separate unbound combo box you could build and execute an INSERT INTO statement in the unbound combo box's AfterUpdate event procedure, and then requery the subform control to show the new item. However, this would undermine the integrity of the database as you would need to allow NULL in the Qty column in the OrderDetails table, or give it a default value of zero. By entering a new row directly in the subform you would normally disallow NULL in this column by setting the Required property to True (Yes) in table design view, and use the ValidationRule property to force a value of 1 or more.