qmail lets each user control all addresses of the form user-anything. Addresses that don't start with a username are controlled by a special user, alias. Delivery instructions for foo go into ~alias/.qmail-foo; delivery instructions for user-foo go into ~user/.qmail-foo. See dot-qmail.0 for the full story.
qmail doesn't have any built-in support for /etc/aliases. If you have a big /etc/aliases and you'd like to keep it, install the fastforward package, available separately. /etc/aliases should already include the aliases discussed below -- Postmaster, MAILER-DAEMON, and root.
If you don't have a big /etc/aliases, you'll find it easier to use qmail's native alias mechanism. Here's a checklist of aliases you should set up right now.
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Postmaster. You're not an Internet citizen if this address doesn't work. Simply touch (and chmod 644) ~alias/.qmail-postmaster; any mail for Postmaster will be delivered to ~alias/Mailbox.
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MAILER-DAEMON. Not required, but users sometimes respond to bounce messages. Touch (and chmod 644) ~alias/.qmail-mailer-daemon.
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root. Under qmail, root never receives mail. Your system may generate mail messages to root every night; if you don't have an alias for root, those messages will bounce. (They'll end up double-bouncing to the postmaster.) Set up an alias for root in ~alias/.qmail-root. .qmail files are similar to .forward files, but beware that they are strictly line-oriented -- see dot-qmail.0 for details.
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Other non-user accounts. Under qmail, non-user accounts don't get mail; "user" means a non-root account that owns ~account. Set up aliases for any non-user accounts that normally receive mail.
Note that special accounts such as ftp, www, and uucp should always have home directories owned by root.
- Default. If you want, you can touch ~alias/.qmail-default to catch everything else. Beware: this will also catch typos and other addresses that should probably be bounced instead. It won't catch addresses that start with a user name -- the user can set up his own ~/.qmail-default.