This is based solely on my Ph.D. research, but I would say that both are quite problematic, with PDFs likely being worth.
Let me explain: When you write an API and invest everything in documenting it, you are able to devote significant attention to each function in turn.
When somebody comes to use your API, or examines code that uses the API, the situation is different. The information needed to understand the call is delocalized - in order to examine it, one additional action must be taken. At a minimum, you have to hover over the call in the IDE to see the documentation (let's assume we're not dealing with polymorphism). In the worse cases, you have to go and open source code, or switch to a different application, or even open a book.
Programmers are naturally lazy and for good reasons - it is completely impractical for us to examine each and every call to learn everything about it. There are just too many outgoing calls, and the surprises are often not where we expect them.
Thus, as an API writer you must assume that the vast majority of calls will never be explored. How much will be explored is not fully outside your control (as an aside, I built a tool to assist with that), but there are ways to discourage an examination. The "best" way to discourage examination is to increase the cost or the latency by requiring an application switch, an active search in the browser, etc. I have seen dramatic differences and avoidance of documentation when a JavaDoc hover in Eclipse took more than 1/2 second to pop up. If the cost and delay is higher (e.g., switch to firefox, load PDFs) you are further decreasing the chances.
In other words, if your users say: "Am I willing to wait 25 seconds for acrobat to load up and then read the docs for the method after I find the page, or shall I just assume I understand what it does", they will go with the latter option. If you reduce the cost significantly (e.g., hyperlink in a browser on a second monitor) you are making the tradeoff more bearable.
I'd be happy to provide more info on this, if it's relevant to your team. Look up my contact info in my profile.
As for what should go in the docs, see my answer on "Tips for great JavaDocs"
If you do Java, you may want to take a look at my eMoose tool (yay for shameless plugs).