Assuming you're using Mobipocket Creator, select the "Guide" page, and add an element with the following properties:
Title: Start Reading
Type: other.ms-firstpage
Filename: book.html#start_reading (or whatever the URL is that you want the book to open at)
Don't forget to click the "Update" button at the bottom of the page, to write the entry back to the file. This adds the entry to the "Guide" section of the OPF file.
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