It depends on the exact code you're writing. But generally--
1. Do your configuration, logic and other preparation in PHP before you output any HTML. (Your first example.)
2. Then go through your HTML layout, and use limited PHP to add in content where it needs to go, such as <?php echo $information; ?> within the right HTML <p> element.
As much as possible, separate your HTML layout from your PHP set up. Sometimes that can be hard if you need to use conditional content, in which can you can either try to use it minimally (for example, store a value to use to check in the IF later, rather than calculating things in the middle of the HTML), or you can look into templating, or even output buffers if you must construct a lot of HTML at the top.
There are certain things that MUST go at the top of your script, such as cookies, so in some cases you will need to do this. In other cases, it's just a good habit to get into.
As a simple rule: if you can put it at the top of your script, do that. If not, see how little you can keep in the HTML and move the rest to the top.
Edit: I was hoping traq would add what he'd written (I just couldn't remember the link). I'd suggest starting there:
PHP & HTML Structure
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