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I personally don't like mdf, but I agree that it is cheaper and paintable. It wouldn't be my first choice for face frames or for large spans (unless you up the thickness to 1" as suggested by cj2112). But if you plan on having painted shelves and don't want the cost of plywood or the look of melamine, than MDF is the solution. That said, I've seen ugly and beat up MDF shelves, so I recommed sticking a strip of solid wood on the front edges of the sides and shelves for function and aestetic. I've seen clear finished MDF shelves with a strip of maple on the front edge that looked great. Also, when you buy your paint, count on using way more than the coverage on the label predicts. MDF is a sponge.
If you do choose MDF, I think it would be tough to follow through with the 'one solid piece face frame'. And it would be more challanging than other matierals to assemble a face frame from pieces because MDF fibers and fasteners don't work great together. A pocket hole jig would allow for concealed screws on the backside and would be cheaper and faster than a biscuit joiner, but you run the risk of stripping screwholes and less than perfect joints.
Perhaps using wood and ply for the face frame assemblies and the doors, and using the same wood type moulding for the shelf edges? You could have your face frames that you could (more easily) assemble via pocket holes, you can make carcasses and all the shelves out of economical MDF, and you can have a nice 'cabniety' look.
As a whole, I would say that mitersaw + brad nailer + 1 forstner bit for the euro hinges is a cheaper and more useful investment and easier process than large clamps + biscuit joiner, assuming tablesaw in either case.
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