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Hello Damien
You need to login to your site.
Click "Administration menu"
Click system admin>preferences>general settings> Preferences main page.
Under Default theme: selector and choose another theme
Under Default template set: Selector and choose THE SAME theme
You can also update selectable themes if you want.
NOW click "GO" at the page bottom.
Go to home page and the new theme will be there.
You can of course upload many more themes and use them on your site. That's another step.
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Adding extra pages: THere are a variety of ways to do this, so I can't really specify what you want. The main guidline is to install a module that will produce the TYPE of pages you want. ie articles, news, FAQs, whatever.
Remember, you can also make custom blocks (of text etc) to display within pages. It sounds like your at an exciting beginning with XOOPS, so May I suggest you experiment carefully and learn the basic steps. Reda the wiki guides, they can be very helpful
GOOD LUCK
Richard