The USB chargers don't output both 12v and 5v at the same time. By default they output 5v and you can have a chip inside the product which negotiates with the charger and switches the voltage to other voltages like 12v.
There are power supplies that output 2 or more voltages but usually come with DIN connectors or other connectors (like miniature pci-e connectors, like the ones on video card)
But it will be easier to use a 12v only adapter with a barrel jack connector, and just add a 12v to 5v switching regulator inside the product, or a linear regulator if the current you need is very low on 5v.