Heya,
Just a few notes. You may get a very slight increase in image quality moving to a new lens from the 85 F1.8. However, "more bokeh" is not exactly going to happen immediately and is dependent on a few factors. Wider aperture will result in more significant out of focus area, but bokeh is not the out of focus area, it's the quality of blur of that out of focus area, and it's completely subjective to you. If you simply want "more blur" that will come from wider maximum aperture (F1.4, F1.2), and/or closer distance to subject (which reduces depth of field). Focal length is simply a means to change distance to subject. And longer focal lengths do have different optical effects on how things render (example: telephoto focal lengths tend to pull the background forward when you are crushing depth of field).
For cost, the 135L is easily the top pick. To note though, longer focal length means faster shutter speed required to maintain a sharp image handheld, so if you're in low light and shooting a 135mm lens, it may force you into higher ISO ranges, depending on how dark your churches and other places are. Something to consider.
Otherwise, the Sigma 85 F1.4 will actually produce "more blur" for the same composition frame up (due to wider aperture plus closer distance to subject). The Sigma 85 and the Canon 85L actually are very similar and neck to neck on a lot of things other than maximum aperture. Rest assured the Sigma 85 is a fantastic lens for portrait and low light.
I would just go ahead and rent a 135L and see how you feel about the distance and focal length. It may be too long. Or maybe it's fine.
Personally I use a manual Samyang 85mm F1.4 lens when I want shorter telephoto with fast aperture. These lenses are $200 and pretty much optically as good as the Sigma 85, just without autofocus. Sharp wide open. Decent CA control considering it's speed too. But I'm proficient with manual focus even at F1.4, with a precision matte focus screen for my view finder (available on 5Dc, 5D2, 6D). Unfortunately these view finder screens are not an option for the 5D3 without getting something custom. That and maybe you are not interested in a manual focus lens, but just to point out, Samyang has excellent manual modern lenses (85 F1.4, 135 F2, etc).
Also, how do you feel about the 70mm F2.8 end of your 24-70? Do you prefer the 85 F1.8 to the 70 F2.8 of your zoom? It's just barely over 1 stop slower and it's a bit shorter, so it doesn't render as potent out of focus blur for certain frame ups, but it's still quite good. But maybe you are really into the super shallow depth of field look. I will warn you, be careful not to get so shallow that you get one eye out of focus, one eye in focus, totally ruins a portrait for some.
I find the 85 F1.8 to be fantastic. I tend to shoot it at F2 and F2.8 pretty often. Still isolates nicely and has awesome image quality.
These are at F2.

IMAGE LINK: https://flic.kr/p/t7DZas
IMG_3929
by
Martin Wise
, on Flickr
IMAGE LINK: https://flic.kr/p/vCRe5X
IMG_4388
by
Martin Wise
, on Flickr
Very best,