The System Mail Settings is a secondary email entered only once by your super user as a backup.
If for whatever reason your personal emails aren't connected or have disconnected (if you've changed your email password etc) any emails sent from Vincere will still send - however they'll send from what is entered in system mail settings by your Vincere super user. This is why it's important to enter a generic business email here e.g. email@example.com or firstname.lastname@example.org.
To setup, head to Settings > Admin Settings > Email Settings
Select 'Edit Mail Settings'.