To set the render image format to OpenEXR you need to set both the imageFormat and imfkey in defaultRenderGlobals. Setting the imageFormat to 51 means that you are going to use a custom image format like Tiff Uncompressed (tif), hdr, exr, Zpic, picture, ppm, ps etc.. and than you set the imfkey to whatever format you want, in my case I set it to 'exr'
from pymel import core as pm
dRG = pm.PyNode('defaultRenderGlobals')
dRG.setAttr('imageFormat', 51)
dRG.setAttr('imfkey', 'exr')
Edit:
Also you can set the compression to ZIP ("Zip (1 scanline)" in Nuke terms) by:
mrG = pm.PyNode("mentalrayGlobals")
mrG.setAttr("imageCompression", 4)
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