The Gimp is a pretty good art package. Its free and supports the PCX image
file format that RND uses.
http://gimp-win.sourceforge.net/stable.html
(you need to download the main package and the Runtime Environment)
When you are installing the main package and reach the "file associations"
page, scroll down to the bottom and check "Zsoft Paintbrush image". Now you
can double click any PCX file in Explorer to edit it.
Its best to look at the main default graphics in RND first, see where everything
is, how it works and make some changes. IMO the best way to learn something
is by hacking somebody else's work
So in Explorer goto your RocksNDiamonds folder and into:- \graphics\gfx_classic\
All the game's default artwork is here in PCX format.
Make a copy of RocksElements.PCX (so we can undo it later)
Now double click RocksElements.PCX to load the Gimp and this image. You should
see a large chunk of the game's graphics, each game element is 32x32 pixels.
Draw on some elements or replace them entirely, and then save it. Now when you run
RND you'll see your graphics instead.

There are other PCX files for different
things, like RocksHeroes.pcx which has Rockford in it.
This is the first basic step, for more control you can for example change the
amount of frames a yamyam has and what PCX image it uses. This requires a
Graphicsinfo.conf file and some text editing. Confedit takes a lot of the chore
out of this process, but I recommend it just for the "create a new RND game wizard"
which will make all the necessary folders and CONF files for you.
Good luck!