If you have the opportunity and budget, buying all your RAM from the getgo is the best idea. If your original budget is restricted or you just underestimated your apps requirements, its is certainly possible to add more.
1. The more slots you fill the greater load placed on your memory controller and you may have to reduce timings and / or speed to obtain stability.
2. Packaged sets are "guaranteed" to work. Though not guaranteed, like factory overclocked and guaranteed GFX cards, you can usually overclock a stock card to factory overclocked levels, but it's not guaranteed. Many of these factory OC'd PCBs are oft not the same (bigger VRMS usually) as the reference PCBs so they do behave differently. Other times the GFX card manufacturer switches from say Samsung or Hynix memory to Elipda and the Elpida based cards won't overclock as well cutting into your SLI / OC performance..
Same with RAM..... with some manufacturer's lines (i.e. Mushkin Redline) you can be pretty confident that the manufacturer hasn't pulled a switcherroo on you. For example.... I just got a new set of Mushkin 2400s and they are based upon the same Hynix memory modules that were in the ones I bought a year ago. On the other hand, the Corsair Vengeance 2400s stopped using Hynix after version 4.51. Mixing two 2 x 8GB sets or the Redlines, I'd be pretty confident they'd work, subject tot he limitations of Item 1 above. Mixing two sets of Corsair's....one pre 4.51 and one after, I'd be far less confident.
3. To show ya how odd and "mixed results" this can be, I was once asked to upgrade two machines that RAM was pretty scarce for. One had two Corsair sticks, one had two Mushkins .... with neither company offering anything of the same spec at that time, I found some GSkills that were a speed and timings match. After advising each user that this might not work, each bought a packaged set of 2 Gskills.
-Putting 2 GSkills in with the 2 Corsairs..... no go.
-Putting 2 GSkills in with the 2 Mushkins..... no go.
To troubleshoot, I put the 4 Gskills in together and they worked .... even maintained speed and timings so figured it just wasn't going to work with mixed manufacturers. But then I put the Mushkins in with the Corsairs and they worked together .... everybody was happy. We got lucky; it won't always work.
So in your case, you are limited to 2 GB per slot..... a set of 2 x 4GB is therefore not an option. 4 x 2Gb is your only real choice to get above your current 4 GB.....don't really see an advantage to the move to 2 x 2GB . Pretty much all I found was Dell RAM meetings these specifications but ECC Types