The answer to your questions depends on what you want to see end up on the page.
If you just want to move the Sign up box a little to the left and nothing more, then it will be one solution.
If you want to move the Sign up box to the left and add another block on an empty space to the right it will be other solution.
Or maybe you want to create the Join page similar to the Facebook Join page, in this case I can suggest you to use these plugins:
http://www.oxwall.org/store/item/601
http://www.oxwall.org/store/item/1027
On the other hand, attempt to move the Sign up box with the use of CSS classes will not work. It's because there are no custom CSS classes for the Join form (Sign up box). And if you change the one non custom CSS class on the Join page, this will make changes sitewide. So these modifications is considered as a custom code modification.
If you are not familiar with the plugin development or code modification, it would be better for you to find a developer who can help you. You can do it here:
http://www.oxwall.org/market/specialists