Hello-
Well, "vmstore" is not a directory, but rather a PowerShell drive (a PSDrive). So, when you cd or Set-Location to "vmstore:", it is similar to setting the location to the D: drive. You could use "cd d:\" to change to the D: PSDrive.
To try to shed more light on this, you can use the Get-PSDrive cmdlet to list all of the current PSDrives in your PowerShell session, like:
PS C:\> Get-PSDrive
Name Used (GB) Free (GB) Provider Root
---- --------- --------- -------- ----
Alias Alias
C 31.76 31.62 FileSystem C:\
cert Certificate \
D 393.04 538.47 FileSystem D:\
...
Function Function
HKCU Registry HKEY_CURRENT_USER
HKLM Registry HKEY_LOCAL_MACHINE
Variable Variable
...
vmstore VimDatastore \LastConnectedVCenterServer
vmstores VimDatastore \
...
Examples of the PSDrives in your PowerShell session: the Windows volumes on your machine ("C:\", "D:\", etc.), Functions and Variables defined in your PowerShell session ("Function:\" and "Variable:\"), the Windows registry on your machine ("HKLM:\" and "HKCU:\" -- HKeyLocalMachine and HKeyCurrentUser), and so on. To navigate to any of those, you can use Set-Location or the alias "cd".
So, you should be able to do a "cd vmstore:\" to initially get to the "vmstore" PSDrive. How does that do?