py26-markdown is not the program's name, it's the name of the package. The program is markdown.py and it comes from that package. It's a module you use by importing it into Python, or by running it from the command line. Using it from the command-line is explained in the user's guide. It looks like this:
<python> markdown.py input_file.txt > output_file.html
You may need to explicitly call it from Python depending on whether it is executable by default or not.
To find out where the actual script lives you should ask port:
port contents py26-markdown | grep markdown.py
markdown.py doesn't necessarily need to be on your PATH, but it will be a lot easier to use it lives in your PYTHONPATH, which should include /opt/local/lib/python2.6/site-packages.