IMHO - DAO is only still around to appease the many users of Access that have been using Access since the 90's. There are many performance issues that are not well documented, and it's transactional support is quite limited in comparison to ADO.
ADO is most definitely the most portable standard - eg .Net and VB6 use ADO (different versions). If you intend to integrate with clustered SQL servers, I would strongly recommend you familiarise yourself with ADO. ADO 2.7 and above provide strong support for clustered SQL servers, which is quite common in larger organisations.
The main issue that most people have with DAO/ADO is that many objects between the two libraries share names. With most coding examples and the Northwind Database itself, fully qualified names are rarely used. By not explicitly defining the library they are using, their code suffers when attempting to move between technologies.
I went through this experience back when I upgraded from Access 97 and Access 2000. Since then I have never looked back. ADO has not caused me any issues and has built a skillset that has been readily transferrable to other applications outside the Office suite.
I have also learnt (the hard way of course) that you should always explicitly reference your objects and never depend on default values or default behaviours. These have been known to change between versions and can often lead to defects that are very hard to identify and resolve.
Anyway, just a humble thought on a quiet Monday morning.
Cheers everyone

Steve