PS Audio Perfect Wave DAC upgrade to DSD?

I have a DSD, and would be hard pressed to find a better DAC out there for the money (and it keeps getting better with each successive firmware upgrade).  PS Audio does offer a no risk in home trial allowing you to weigh the virtues of a new DAC while you audition speakers.  In my case it was a significant upgrade in sound over the DAC in my Oppo UDP-205 player.  However, if the sibilance is intrinsic to the speakers, you’d be best served upgrading there first.  

My understanding of sibilance is, that it might belong to the recordings, but when we use the term, we are thinking about too much sibilance, that sounds aggressive. And it mostly is not just stronger high frequencies. I think, it is a form of distortion and this can have many reasons.

I was strongly suffering from sibilance too, upgraded speakers (from electrostats to Living Voice IBX R3), my amplifier (now Lavardin ITx), my DAC (now Lampizator Baltic), my music server (now Innuos Zenith Mk3), my cabling (all Lavardin). Of course the jump from electrostats to Living Voice was a big jump as would maybe be with the bright Thiel, but it did not erase any sibilance. Just the presentation was a little easier to my ears, but none went way. And the same is true for all other upgrades.
What did a lot more in erasing sibilance:
- Additional carpet to cover more of the solid wood floor
- EM / RF treatment "voodoo" radiating Obsidian pieces and stickers on all glass (Vortex Hifi) 
- Cleaning power ... and the recent winner for this area is:
.... A Power Distributor with an included "Firewall" custom made from LessLoss
.... And a "Humbucker" power cable, which eliminates incoming EM / RF made from the same LessLoss

Visit their website and you will find my recent reviews.
The burn-in time is awkward, but after 4 weeks I enjoy it all. Sibilance is cut down very low and the remaining is connected to the voices and not just jumping at me. And it has a lot more ... powerful controlled bass, fantastic soundstage, rich sounds ...
It worked great for me, but I have very bad power coming in and plenty of Wifi radiating into our house. So might not be the same for you.
The total of my EM / RF treatment and power improvement cost about half of the electronics, speakers and cables, and I feel, it was worth it!!

Sorry, that I moved the topic away from DSD upgrade vs. speaker replacement :)

Lots of good advice, thanks all.  About a year ago, after putting this first system together, I came up with the following long term plan, based in part on other posts and responses and reviews etc, with the goal being to slowly improve SQ altogether and hopefully reduce the high end smear.  I know that the most direct route might be to replace the speakers, but I also wanted to learn through experience how other changes could affect SQ through the Thiels. 

Here's the plan - 
1) upgrade power cords, receptacles, maybe the conditioner.  I have done all I plan to do there, but the posting above might make me reconsider a different conditioner (would love a PS Audio regenerater but I think SQ/$$$ will be relatively low compared to other improvements, at least at this point).
2) Work on room treatments - this is an ongoing work in progress. I have absorption at primary reflection points, including a heavy wool carpet, added isolators for the speakers and components, ditched the rack and coffee table, read some Jim Smith, etc. This has helped tremendously and I've got a few more improvements lined up over the next 4-6 weeks.
3) Upgrade the source (hence this post) to the best in my budget.  I bought the PWD with the DSD upgrade in mind.
4) Don't mess too much with cables, interconnects, or preamp - I think these are fine tuning adjustments best done when the components are in place, kinda the icing on the cake.  Although seriously thinking about a Supra Cat 8 ethernet cable for the DAC's bridge.
5) Either upgrade speakers or the amp - I am leaning toward higher efficiency speakers, but it will take me a while to figure out which ones, Zu, Joseph, Devore are all contenders but I have heard none of them auditioning will be very hard, hence the choice to do #3 first.

If you're otherwise happy with the speakers, I would consider upgrading the crossovers in your Thiels.  Better capacitors on my speakers (Duelund CAST Tinned Copper on Coincident PREs) eliminated some light smearing and brightness/sibilance in the highs.  There are some threads on Agon documenting the process for Thiel speakers, and I think Jim Thiel's son will actually help you with the process if you contact him (it either happened in the Thiel owners thread, or those folks will know how to contact him).

I'm clearly getting a different experience than others, but I've upgraded my PWD MKII to a DSD twice and both times ended up going back.  I don't know what it is about the DSD that doesn't work for me, but that's been my experience.

cal3713 - talk about striking a chord!  The first response I got when I posted on the Thiel Users thread was an enthusiastic "upgrade your crossovers!"  Tom Thiel (Jim's brother), Beetlemania, a couple other happy modders are fine tuning the design(s) and one day this upgrade might be available through a tbd company or Coherent Source, the post OEM repair/parts/service provider for Thiel.  If I a) had a second pair of speakers and b) knew how to solder, I would be in with two feet bc the trial runs are showing excellent results.

The Thiel thread is one of my favorites - excellent history, design, and anecdotal info re all things Thiel, mostly provided by Tom Thiel himself; lots of good user tips (best amp pairings, how do I fix...., relative virtues of the different models, etc), and although some might perceive small bits of smuggery about the users' preferred speakers, there is NONE of the trolling that sometimes enters into online hifi discussions.  And I have come to trust the listening, interpreting, and writing skills of many of the contributors. Highly recommended and one of the reasons I want to stick with the Thiels!     

All that being said, bummer about the PWD vs DSD - you are the first I have heard having this experience.  What changes for the worse?