There is no point in changing/adding the 95, 465 ports in the Internet Mail program as avast can't monitor SSL/TLS secure email traffic, that is the whole point.
The difference is, in MS Outlook (not express) the avast outlook/exchange plug-in works within the email client and as such can monitor the traffic.
I'm a little confused by question one, the Outlook/Exchange (plug-in) is for the MS Outlook or MS Exchange email clients and nothing to do with servers.
If you are only using MS Outlook and no other pop3 email client like OE or thunderbird, etc. then you don't need the Internet Mail provider.
You don't say what version of avast you are using, home or pro. The scheduled scan options are only available in the Pro version.
Check this work around out -
HOWTO: Scheduled Automatic Scans avast! Home Version!The major disadvantage with the task scheduler trick of using ashquick.exe is, it will scan every file of the hdd, partition, folder or file that you set it to scan; even those files not considered a potential threat, this can take a long time. It is possible to add certain folders to the exclusions list for say your media files, etc. This could leave you vulnerable if that folder got infected as it wouldn't be scanned by the on-demand scanner as you have excluded it.
The Pro version gives a lot more flexibility and the scan would follow the settings and exclusions, etc. of the regular scan.
With the different levels of protection of and the fall back of the Standard Shield, I find the need for daily scheduled scans lessened. I prefer to do a manual scan with my regular weekly maintenance tasks.