Make Theme Options Menu item more easily / directly accessible

Theme Options page under Appearance are added by this function.

<?php
add_theme_page( $page_title, $menu_title, $capability, $menu_slug, $function );
 ?> 

To make it appear outside as a top level menu page replace it with following.

<?php add_menu_page( $page_title, $menu_title, $capability, $menu_slug, $function,$icon_url, $position ); ?>

Where

$page_title :The text to be displayed in the title tags of the page when the menu is selected.
$menu_title :The text to be used for the menu
$capability :The capability required for this menu to be displayed to the user(for add_theme_page generally ‘edit_theme_options’ and for add_menu_page it is ‘manage_options’).
$menu_slug : The slug name to refer to this menu(it should be unique.)
$function : The function that displays the page content for the menu page.
$position : The position in the menu order this menu should appear.

Reference:

Add sub menu page to the Appearance menu

Add a top level menu page