Since it's your first trip to DL, I will assume you know very little and make some general comments. I am planning our first trip to WDW in May, and have come to realize some differences between DLR and WDW that are worth noting.
1. The dynamics of parkhopping are completely different. DLR only has two parks, so that is one big difference. But the two are so physically close that you can easily hop back and forth - even multiple times on the same day. Plus, the hotels are so close it changes some dynamics there as well. It is so easy and time effective to get back and forth to your hotel, it just begs for long, relaxing breaks in the afternoon. At WDW there are more obstacles to this - you have to catch a bus or a boat, and it takes longer in general. Do the same things at DLR you would do at DLR: Get to the parks early - 20-30 minutes before opening, take a long hotel break (ours were 4-5 hours, with 3+ hours naps on most days), and come back in the evening to use your FastPasses, do some rides, and see some shows. Stay as late as your group can make it.
While some people insist on comparing DCA to DL and identifying all of its faults, it's proximity to DL and hence easy parkhopping has made it appear to be like another DL "land". You know, TomorrowLand, FanatasyLand, and now CaliforniaLand. So DL and DCA are to my family and many others just one big park. Viewed this way, it is a good addition to DL. The fact that parkhopping is included for "free" in your DL tickets reinforces this idea.
2. Transportation - similar to point 1 above. We have stayed at the DLR PP hotel and at good neighbors, and as long as you are close enough you will never need to get on a bus or tram all week (except when you head to Hollywood, obviously). We walked everywhere last August and never got in our car or a bus, taxi or tram.
3. If you have an idea to stay at a DLR hotel, if you book it through AAA you can then you can get Enhanced FastPass. IMO this is not as big a perk as some people make out, but if I was going to stay at a DLR hotel I would get it if I could. If you have not heard about it, this link discusses it and FastPass in general:
http://mousepad.mouseplanet.com/showthread.php?t=43193
4. If you have used FastPass (FP) at WDW very much you know it can really make a big difference and you should work it into your plans when you can. The DLR FP system has several loopholes that do not exist at WDW. This link I wrote based on our DLR trip in August 2005 gives an exhaustive discussion of this:
http://www.disboards.com/showthread.php?t=885132
To summarize some of the loopholes that do exist at DLR but not WDW:
a. There are "disconnected" FP rides at both DL and DCA, which means the FP return times do not affect other FP availability. I believe that Roger Rabbit at DL and Grizzley River Run at DCA are the only two at present.
b. The acceptance of expired FPs from the same day has been policy at DLR for many years. In 2005 on several occasions we used FP we got at 8AM (with return times of 8:45-9:45AM) and used them at 11:50PM that night with no problem whatsoever - 15 hours late.
c. Unlike WDW, when you enter either DL or DCA, your entrance tickets are initialized for both parks at the same time. If you are in to picking up FastPasses and parkhopping, you can enter one park and then send a FP runner to the other park to get FPs without everyone needing to enter that park.
5. Early Entry has some similarities and differences at DLR vs. WDW. First, only DL has it and not DCA. Second, it is pretty regular which days it occurs and what rides are open. The DL EE has no impact I can see on DCA. But if you are not going to use EE at DL on an EE day, that is an especially good day to start the morning at DCA. If you go to DL on an EE day and you do not use EE, you just need to avoid FantasyLand that day and the impact elsewhere will not be significant as long as you FP Space Mtn and Buzz LY.
6. Do some research on viewing locations for Remember Dreams Come True fireworks. My youngest two were 9 and 10 last summer and we wanted to see it from the hub. Most everyone stands up during the show, which can make it hard for kids to see unless you hold them. I got a spot on a curb in the hub so my youngest could see over those standing in front of them, and this worked out great for us.
7. Like WDW, there are some rides that are worth doing in both day and night because of the difference in experience. Here are a few off the top of my head:
a. Matterhorn
b. BTMRR
c. Splash Mtn
d. StoryBookLand Canal Boats
e. ToT at DCA
f. California Screamin at DCA