I wondered the same thing. I am a huge fan of TNG so I actually started there.
Once I watched all the TNG, though, I decided to start with Enterprise and then go in the order they fall in the timeline from ENT all the way through Voyager including the movies. For example, I even will rewatch the In a Mirror Darkly where it fits with the Tholian web in TOS. There was a series of posts to this effect a while ago. I went ahead and put it all in a spreadsheet so that I can organize the order I will watch.
Since I have Netflix, I have already put them in order in my viewing queue. In fact, if anyone wants, I can forward my simple excel spreadsheet that shows the discs as they are organized.
Once I watched all the TNG, though, I decided to start with Enterprise and then go in the order they fall in the timeline from ENT all the way through Voyager including the movies. For example, I even will rewatch the In a Mirror Darkly where it fits with the Tholian web in TOS. There was a series of posts to this effect a while ago. I went ahead and put it all in a spreadsheet so that I can organize the order I will watch.
Since I have Netflix, I have already put them in order in my viewing queue. In fact, if anyone wants, I can forward my simple excel spreadsheet that shows the discs as they are organized.