I would say a Dac upgrade would likely be more noticeable and beneficial than a streamer upgrade.
Adding a better DAC to the Node 2 I had (not the Node 2i) did improve sound quality. The ones I tried were the Auralic Vega (which was $3500 when new), the DAC in my Sony TA-ZH1ES headphone amp (which is very good), and the Mytek Liberty DAC. They all sounded better, but not great.
When I replaced the Node 2/Vega combo ($4K of gear when new at list price)
with the TEAC NT-505 ($2K) streamer/DAC there was a very noticeable improvement in sound quality, much greater than the improvement that came from adding a better DAC to the Node 2.
So I'm guessing... but based on this experience I think both the streamer and DAC matter and that with the amount you'd have to spend to get the Node 2 to sound better, you're better off stepping up to something like the TEAC, Lumin D2, or the Lumin UI Mini if you already have a good DAC.
If you already have a good DAC, it should make the Node 2 sound better, but probably not as good as a better streamer paired with a decent DAC (or a streamer that has one included) will.