Neither certification is marketable of itself. Certification makes YOU more marketable by showing that your skills meet some known benchmark. A paper certification with no experience to back it will not magically double your income. (Nor, for that matter, will a certification WITH experience to back it.)
Start with what you know and with the equipment you can put your hands on. You will need equipment to practice on while you are studying, and more is better.
If you are an experienced Novell admin, you should be able to easily pass the first exam based on what you know. Based on that you can decide whether or not to continue.
If you are experienced in Win2K, pick one exam, study for it, and take the exam. Passing one exam gives you MCP, and you can then plan what you want to do. All reports indicate that Microsoft has made the exams harder in an attempt to get rid of "paper MCSE's" so prepare carefully.
If you are really at ground zero, you might want to think about finding a job with some employer who will pay to train you and where you can pick up a lot of on-the-job training.
Good luck.