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What I have found in Outlook is that there is no "maximum" number of emails that can be stored in the .pst file, but the larger it gets, the more likely you are to see corruption in the file itself (the .pst is still essentially a database that manages all the information and emails, and computer crashes with the email client up can have an adverse effect on the stability of that file). When the .pst is finally too corrupted to be opened and used, you will have a problem opening Outlook.
Should that happen, the best thing you can do is to be sure you have a backup of the .pst files, and to try to first run scanpst.exe on the .pst files and if that doesn't resolve your problem, go back to your backup.
In my home use of Outlook (and, I'm assuming, OE) I've seen that the client sets up it's own .pst file for the files downloaded from POP servers, so the same rules should apply.
Regarding the spyware scans, you mainly don't run multiple scans at the same time because you don't want the applications to accidentally try to grab and lock the same file at the same time. Scans can also be resource-intensive, so if you don't have plenty of RAM and a good processor, you can slow the machine way down. It shouldn't really matter much in what order you run the scans (though I plead ignorance to running AVG antispyware scans). I've seen no difference in running either order with Spybot and AdAware. They search according to what's in their signature file and each will find some things that the others don't while both will find some of the same things: whichever program you run first will find all or nearly all of the common vulnerabilities in their signature files and the second scan will pick up the rest.
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