This is what I have gathered in Bond LD knowledge over the past couple of months:
The general consensus on this thread is that the Connery films are best in the Connery Collection volumes (I and II) because they were pressed a few years after the 1989 series. These can be had for around $10 each on ebay (I just received Vol. I for around $7) The first three were initially available on Criterion but despite originally having banned commentaries the transfers have paled in comparison to others.
For OHMSS through Licence to Kill your only option is pretty much the 89 series with a couple exceptions.These can be had for around $5-10 each. Also, make sure that it says Deluxe letter-box edition on the top because an earlier run of fullscreen transfers uses the exact same artwork.
Goldfinger and Thunderball had deluxe box set releases in the mid 90's and those are tough to beat. They edge out the Connery Collection transfers. (they do cost more than the others-I'd check the others first.)
Dr. No, FRWL, Goldfinger, Thunderball, The Spy Who Loved Me, and Moonraker all had THX certified releases in 1998. These are the last Bond catalog title releases on LD in the US and are extremely rare. They all resemble their initial THX DVD and Special Edition DVD counterparts.
Licence to Kill was initially released on Fox LD as a 2disc Letterbox LD. I have this and it isn't bad, but it is prone to rot and is not the uncut version. It was later repressed as part of the MGM series and this one does not rot like the Fox. For an uncut LD I think you have to find a particular German or Japanese one.
Goldeneye and Tomorrow Never Dies were released on seperate Dolby Digital and DTS versions. The only difference between the two is that the Dolby LD has 5.1 @384kbp/s and the DTS has the full 1565kbp/s DTS 5.1. If you have a DTS capable setup then that one is the way to go definitely. the dolbys go for around $5 and the DTS go for around $30-50. Both feature the original theatrical soundmixes and not the remixed ones found on the UEs.
Finally, The World is Not Enough was released on LD in Japan. It has a Dolby EX 5.1 track.
Whew!
So in short I'd guess I would recommend going for the title you are most interested in first as a test. The best place to start otherwise is one of the Connery collections and a few of the 89 series. This won't set you back too much and they pop up on ebay very often.