No problem; I love doing this kind of stuff!
You should be able to bring your domain over, but you'll need to have that domain point to the two 000webhost nameservers:
ns01.000webhost.com --AND--
ns02.000webhost.com
You might have to call customer service to switch them for you.
As for 000webhost, it should come with both. You should get a webserver with PHP and the ability to have 2 MySQL databases when you create your site. You'll need to create a database and user for phpVMS, and make sure they are associated with full priveleges. I'[m not sure where you came up with the two options, but the registration form at http://www.000webhost.com/order.php doesn't seem to have that. Both servers should be available to you right away via your cPanel. You shouldn't need to configure PHP at all.