Word is a lousy web editor at best. FrontPage Express is capable, but if it's templates you are looking for you won't be any further forward with it than you are with Word.
An excellent site that deals with FrontPage Express and all versions of its bigger brother (FrontPage) can be found if you click here
You can extract FrontPage Express from an old copy of Internet Explorer and use it on Windows XP, if you really must.
Web editors come in all shapes and sizes. If you want a WYSIWYG editor where you work on a page and type text and add images directly onto it, your options are a bit limited. Check out magazine cover CD's for older versions of NetObjects Fusion and similar web editors. They may be a couple of years old, but the programs still work well and often have some nice templates to get you started.
If you want to be adventurous you can download AceHTML 5 freeware from click here
Note that this is not necessarily a simple editor but it is very capable. It's a good start if you want to learn the underlying code of your web pages.