Yes, you can add on other domains by going to the Control Panel and setting this up. I'm assuming Blue Host uses cpanel like Hostgator so when you login, there is an option to add on other domains. I've never used Blue Host so I am not familiar with the exact steps but I'm pretty sure it's possible.
You can definitely use your PS designs with WordPress, but importing them into the WordPress platform will require you to learn a bit of CSS. If you don't, it will make the process kind of difficult. For most WordPress themes, the design is broken up into multiple files. For example, if you want to edit the header, you need to edit the header.php If you want to edit the footer, you have to open and edit the footer.php.
I use the WordPress Thesis Theme (not free) and one great thing about that theme is you can use their custom functions file to manage your entire blog. So I no longer have to open multiple files to edit various sections of my blog. My entire blog design is managed by updating one PHP file (and my stylesheet). Nevertheless, knowing CSS is really the first step because it will be difficult to explain without having a basic understanding.
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