You can pick a core style (the way the menu works and displays) for the Start Menu - Classic (single column), Classic with two columns, or Windows 7 style. Then for each style, you can go to the "Skin" tab and radically alter the appearance.
The Explorer toolbar buttons can only be at the center as Ivo said if they are on the same row as the menu bar. The menu bar is not available everywhere in Windows 8 and above but can be enabled by using tools like Ribbon Disabler (
http://winaero.com/comment.php?comment.news.20).
Here are some icons you can get for Move To/Copy To buttons:
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