Hi Devin,
Great question. A few years ago I would have told you to move forward with HTML5 cautiously, but the new standard, and it is a W3C standard how now been implemented across the most popular browsers.
HTML5 has many advantages over 4.01 HTML. There is the addition of many new tags or elements and with those new tags came the implementation of many new features that were not available in HTML 4.01.
As an example, on many of the sites I have written video played an important role in the site design. With HTML that required plugins in order to implement, now in HTML5 we have a new video element that allows the direct playing of video in the browser. Granted if the users are using an older browser you may need some fallback code for a short while but that is becoming less and less frequent.
We also have the canvas ability which is a popular feature.
There are many new structural elements in HTML5 that allow for a much more semantic markup of the content. That improves SEO and site rankings if properly used. There are just so many new features in HTML5 I cannot imagine why anyone right now would be structuring their markup using the old HTML 4.01.
I imagine there still are some people that use the old structure but they are hurting their clients by not taking advantages of all the new features and possibilities in HTML5.
I hope this helps.
Mike