LR is really a very good program to teach reading. I used it exclusively with my son from 4 to 12 months with awesome results. Just make sure you print out the words and read them often besides watching the lessons.
Adding other programs is also useful. You can start with Starfall.com to master the letters and letter sounds. After that, you can move on to readingbear.org. You can also watch Preschool Prep Co DVDs, if you have an iPad/ iPhone, you can use their apps for shapes, colors, numbers, letters, sight words, phonics, etc. Another awesome app is Bitsboard along with all the other Grasshopper apps.
Signing time is good for sign language and vocabulary. The DVDs are available in most local libraries in the US.
You can add Your Baby/ Child Can Read and your baby/child can discover. Check out ebay, they're always on sale there.
In a later stage, you can add Readeez.com videos
Also, lots of books and games. Let your toddler watch you teach your older one. He/she can learn effortlessly.
In my opinion, an abacus (RightStart or Slavonic), puzzles and Legos are must-have toys for that age. Math and many other concepts can be taught.
Finally, read the older posts on this forum, you can find priceless pieces of advice and inspiration. You may spend hours and hours reading, but it's worth it
Happy early learning!