Blocking an unknown program from accessing the Internet

Recently I received several (60+) bounced emails containing apparently malicious links which I did not send, however they have my address as the originating address.

These emails went out to my AOL address book. My outbox on my computer does not show these, but they do appear in my online "sent mail" folder.

I was online to AOL for the brief period (3 mins) when this happened (that was on a backup computer).

I am running MSE and Windows Firewall (both active and on) under Win7 on my Dell Notebook.

I have a full scan going now.

Questions:

1, Will MSE scan find the program which sent the emails?

2, How can I set windows firewall to stop unwanted programs from accessing internet?

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