Yes, you can start services on the different accounts in the Properties of SQL Server on the Security tab for SQL Server and in the properties of the Agent on General tab for the Agent.
As for the setting Email Operator I think you need Exchange server on the network or at least Exchange Client or Outlook Client. For Net Send netsend should be enabled in the domain, ask your domain admins. You set this up when right-click on the Operators and select new Operator. SQL Mail should be configured for testing operators.