After you install the connector and start outlook a wizard kicks in asking
for your email address etc. To add a second, follow the wizard that comes up
when you click the button to add a new account in tools, accounts.
On the second question - I'm not totally sure I understand the problem. If
your website has an email server you can configure outlook to collect the
mail from it. If the website doesn't offer email accounts, then you need a
host who offers email too.
If you want people who visit it to be able to send you email, you can create
a link in the format of mailto:
[email protected] - visitors can click it to send
you email. Note that this will result in a lot of spam.