If you do NOT check the box to enable the 5 GHz network to use a different name, then both the 2.4 GHz and 5 GHz networks will use the same name. Devices will then choose the best network to which to connect based primarily on the signal strength of the wireless signal.
This all sounds good in theory, until you realize that the higher frequency 5 GHz signals are significantly weaker than 2.4 GHz signals, so devices are usually going to favor the stronger 2.4 GHz signal when they look for a connection.
If a device is 5 GHz capable, and it is located in the same room as the AirPort Express, or it has line-of-sight with the AirPort Express, it has a decent chance to connect to 5 GHz when both bands are using the same wireless network name.
My Mac laptop does a good job of connecting to 5 GHz when it is in close proximity to the AirPort router and to 2.4 GHz when it is a room or two away of the AirPort, but your results may not be the same.
If you want to insure that a device connects to 5 GHz, the only way that you can really make this happen is assign a different name to the 5 GHz network and then "point" the device at that network. But....and this is a big BUT.....simply connecting to 5 GHz does not automatically insure that you will be connecting to the best quality signal, so you will need to do some experimenting to find out what might work best for you.