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Starting cmd.exe

Using the (default) shortcut file

cmd.exe can be started by pressing Win+R (the Windows key), then typing the three letters cmd and hitting the ENTER key.
This method will (typically) find the shortcut (.lnk) file Command Prompt.lnk which is located in %APPDATA%\Microsoft\Windows\Start Menu\Programs.

Changing the initial directory

If cmd.exe is started using this shortcut file, the initial directory is determined by the .lnk file's property Start In.
The property dialog, that shows the available propertes and their values, is opened by pressing alt+enter with the .lnk file selected in explorer:
In this picture, the Start In value is empty, thus when cmd.exe is started, its initial directory will be C:\Windows\System32.
This directory can obviously be changed by entering a new directory in the dialog box. However, it is also possible (and imho less error prone and less time consuming) to change the initial directory with PowerShell):
$sh  = new-object -com wScript.shell
$lnk = $sh.createShortcut("$env:appdata\Microsoft\Windows\Start Menu\Programs\Command Prompt.lnk")
$lnk.workingDirectory = '%homedrive%%homepath%'
$lnk.save()

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