Unless the ebook is created with a page that has an image of the cover on it... the answer is no. The cover is usually only part of the metadata in a mobi book. Which means you can't open it to the cover... anymore than you could open it to the author.
Short of converting and/or editing each of your books to include an inline image of the cover as the very first page (as Sydney's Mom suggestion will do), the book will open (the very first time) wherever its creator decided it should open and there is no Kindle setting to override that. Each book has its own "Start Here" built into it.
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