I feel like I sensed this question or something..
Starting with either Classic Who or Nu-Who is a widely-debated topic, so it depends on preferences that might not be known until you start watching. Some say you couldn't possible have love for Who as a whole unless you started with early incarnations, but that is just silly. I was exposed to some CW as a child, but it was not until I sat down to some PBS on a very bad night in 2008 (and lucked into a DW marathon on PBS) that I was in love and so very entranced. Yes it is kitschy in places, especially in earlier NW episodes, when the budget was skeleton at best. But it is so, so worth it. It gets better with each regeneration of the Doctor, and you will laugh, cry, and laugh while crying. You might also find yourself screaming, "Moooooooffffffffffat!"
(I love you to death Miss Leela, but) please don't watch Vincent and the Doctor out of order. It is good as an independent episode, but there are nuances that I cannot spoil that will make it great if you watch it in order, as part of the time of the Ponds. (Also know that it has made grown, burly men bawl like babies.) Blink is an okay episode to watch as a single installation though.
I feel like there's so much more I could add, but I also know that I've probably already typed too much. It's not a secret to anyone that I adore DW, so I tend to get all giddy and blabbery about it. Then again, it did literally save my life, has allowed me to process several traumatic occurrences in my life in a more promising way, and has given me a hero to believe in-one that will always "an optimist, a hoper of far-flung hopes, and dreamer of impossible dreams", which helps me find the hero within myself when needed.
Shutting up now, but I'm so excited that you've decided to hop aboard the TARDIS!
