"network user accounts" can mean (at least) three things:
An Active Directory user account, but without configuring a
roaming profile
An Active Directory user account, with a roaming profile
An AD user account with a home folder mapped (by GPO or via the
user's properties)
In the first case:
Your user has a local profile only, when he logs on computer A for the first time, the profile is created, and when this user logs on computer B for the first time, another profile is created (in C:\users)
The profile is not stored anywhere else because nothing instructs Windows to do so.
In the second case:
The roaming profile is downloaded (or created if it's the first logon) on the computer (in c:\users) from the fileshare, when the user logs off, the downloaded profile is merged with the profile on the fileshare.
In the third case:
In this case, you chose to map a network drive for the user, when the session is opened, Windows does nothing more than mapping the wanted drive letter to the folder on the fileshare.
So, your question is, why the profile is not directly mapped on the fileshare/drive letter but remains in c:\users ?
Because there would be a lot of performance issues, there is a lot of activity in the user's profile:
the current user's registry is stored on that folder, imagine if this was on the network share, there would be a huge latency when enumerating the current user's registry (for example).
And what happens if the network connection is lost ? No more Desktop ? A lot of applications will wait on countless timeouts because the user's profile is unavailable (AppData is in the user's profile too, a lot of applications use this location to store user-specific settings)
Howver, don't forget that you can use Folder Redirections, for example to redirect the user's Documents folder on the network share that you want.