Hi tallereric,
both numbers look correct, but they refer to different denominators which is why this can be confusing.
An app's CPU usage is measured in terms of "how much of a single CPU core does it use?". That's why the CPU usage of a process in this view can also go above 100%. E.g. 300% CPU usage would mean the process uses as much CPU cycles as 3 CPUs can provide (it might still be running on 6 CPUs for 50% each).
However, the split in System, User and Idle is measured in terms of total CPU cycles the system can provide. You can also see this difference in the Xcode view: The left-most number on the gauge is 1200, indicating that the maximum CPU usage you can have is 1200%. This indicates that the system you are measuring has 12 CPU cores available.
You can now take the 23% of a single CPU the app uses and divide it by 12 to arrive at the share of the system's CPUs the app uses: 23%/12 = 1.9%, which fits into the 5.13% of user CPU usage you see.