Well, that cheat sheet contradicts itself in that at the top left it shows < and > as being "anchors", then at the bottom right shows them being "escaped" as literal characters for HTML tags.
The only special use of either of them that I can think of in PCRE regexp's in PHP is in look-behind assertions and named sub-patterns. In those cases, the position in relation to other characters determines if they are being used for those special purposes.
That being said, it doesn't particularly hurt to escape them if you think there could be any ambiguity/confusion, but in most cases it won't be necessary. And you can always let PHP do the work by using the [man]preg_quote[/man] function to escape characters used in string literals:
$search = "a bunch of text with lots of characters: <>.,/^!@#";
if(preg_match('/'.preg_quote($search).'/i', $text)) {