I've never explored them, but I believe there are plugins and curves you can get (I've heard about curves mostly when talking about Nikon though). With some work, you could probably try to approximate Velvia, but I think you'd be hard pushed to get it exact, I'd be interested to see any results that people have though. From some experiments in recent years, Velvia has a unique look that I have never been able to reproduce, especially in the blues and greens. That said, I have more expertise with Photoshop now than I did the last time I tried, but even now, I really only do enough to get by. I really must use up my Velvia film before it goes off.
As for lenses, the TS/E has the advantage of sharpness at wider apertures, but stopped down to f/8 and beyond, the 24 f/1.4 MkII is equally as sharp according to tests, although I haven't compared the two. Personally, I like what I've seen with the 90mm TS/E, but most of what I've looked at with that lens has been near macro or closeup shots, where the corners wouldn't matter. I sometimes use my 135mm for landscapes, it has a different look to my 24 f/1.4 MkII and not just in terms of focal length/FoV. I also use the 50 f/1.4, but the tones aren't as nice as the 24 (or the Zeiss 21 from what I've seen during my previous research before settling on the 24).