It depends on a lot of stuff.
It's very difficult to get right into a tax group at a big law firm. Having an LLM will definitely help a career in that area of law. If you are dying to focus on tax and have a knack for it, then a part-time program could be a good idea.
If you have the job, speak with a few partners at the office and get their take. Maybe they will even be willing to pay for it.
However, if you have a Biglaw job, the worst decision one could ever make in the current economic climate is to leave and do an LLM full-time. I know you didn't ask about this, but I actually had a friend who was considering it. She even got into NYU and I still told her absolutely not.
I know a few people who went part-time and their lives were miserable. People underestimate the commitment an LLM involves. I found it much more difficult than law school. These people were working 8-4, then going to class from 4-8, and then going back to work until at least 11. Granted it was only 2 days a week, but that would be your life for 8 months out of the year for 3 years.