... And, more generally , the rear mech will pull forward in every gear whilst using the large chainring if it's at 90 degrees when in the smallest sprocket - is that a good idea?
That is right! I'm using 50/34 and 11-28 cassette and it is very close to 90 degrees.. When using 50T and 28 combination (big ring/big cog), the rear mech pulls forward almost straight. However, it won't be a problem if your chain is not shorter than the number of links recommended by the calculator.
What happens is when you use the largest chainring and the largest sprocket a lot of noise will be generated due to the chain rubbing the front mech. That is "cross-chaining" (using the smallest rear cog with the smallest front ring, or the largest rear cog and the largest front ring)
Bicycle chains are quite flexible, and will work fine with any combination. Even knowing they are there available to be used and can work ok, these combination should be avoided.
As I mentioned my is very close to 90 degrees (after shortened my chain due to crankset and cassette replacements) I had to remove 3 links totalling 53 links.
I just used the calculator which recommends 53. Both methods work fine..