If you're just getting started, I strongly recommend reading the Tutorial/FAQ's. They're easy reading of very important concepts for managing your Zen Cart store.
Look in:
includes/templates/YOUR_TEMPLATE_DIR/common/tpl_header.php
where you see:
Code:
<?php echo '<a href="' . HTTP_SERVER . DIR_WS_CATALOG . '">'; ?><?php echo HEADER_TITLE_CATALOG; ?>
Change it to:
Code:
<a href="http://www.YOURDOMAIN.com/">Home</a>
You may want to leave that original code shown above and rename the link in the language file:
includes/languages/english/YOUR_TEMPLATE_DIR/header.php
change
Code:
define('HEADER_TITLE_CATALOG', 'Home');
to
Code:
define('HEADER_TITLE_CATALOG', 'Store');
note: Text could be anything... 'Store', 'Store Home', etc...
That would leave a link to the main ZC store index page and then you ADD the additional static html link you create to your html 'Home' page (non-Zen-Cart page).