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-login %u %p - This logs into Steam with the specified Username and Password combination. Replace %u with the username, and %p with the password you want to login with (Steam must be off for this to work.)
Source: http://developer.valvesoftware.com/wiki/Command_Line_Options#Steam_.28Windows.29
If you still want Steam to automatically startup, while logging in to the appropriate account, disable automatic startup within Steam and place the shortcuts in the Start menu-> Programs -> Startup folders of each windows account.