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This is my first attempt at painting a whole army, and the practice models of space marines I've painted with white power armour just have not turned out right. Either the recesses weren't distinguished enough or the white came across as rather murky or unshaded. Admittedly im improvising with my paints, using old variations and dilluting my abbadon black rather than using nuln oil, but i dont feel thats the issue, although It'd be an easy fix if it were. Do i just not have enough experience to try out an improvised colour scheme rather than the official chapter colours in the codex? or should i be looking at a guide on space marine painting and go through all the paints used and switch them with a white version? how can i get around this?
Id love to see some examples of other predominantly white armies for inspiration

Painting white is always a bit awkward, if you can get some shots up of the mini's you are having issues with we can have a look and see if there is any easy enough fix for them.

Generally you would want to stick with a relatively light grey for the undercoat, then highlight up to white in at least 2 coats. If you feel the recesses aren't dark enough with that you can add a light shade with a wash and then rehighlight up to white again.

Just be sure not to make the mistake of trying to paint white over black or a dark grey, or trying to get to white in just 1 layer.

I recommend just starting with a white undercoat and then painting light grey into the crevices, OR very lightly painting Black Wash into the crevices using a detail brush (not the finest detail brush, but just something fine enough that you can manipulate it into the crevices without making a mess).

Another way is to do a white undercoat, wash the entire model with a light coat of Nuln Oil, and then go back over and paint the model white, leaving the Nuln Oil in the crevices.

The latter method looks slightly nicer IMO, as your eye can tell which layer went on first and which layer went on 2nd, which makes it look a bit unnatural when you paint the crevices AFTER painting the basecoat (in this case white). Also, sometimes when you paint wash on like the first method you get dark lines around where the wash was applied. However the first method is a lot faster, and it might give you the look you want anyway.

Personally I use a mix of the two methods, undercoat white, paint Nuln Oil into the crevices but don't stress about being too neat about it, then go over with some Ceramite White and touch up the transition between the dark and the light.

The main thing to remember with white is just focus on the shading, because you don't have a highlight, you have the basecoat of white and then no highlight. If you wanted something that looked neater, instead of using the black wash you could just use a light grey and carefully paint it into the crevices, doing it in 2 or 3 layers to give a smooth transition.

It all depends how much time you want to spend on it.

EDIT: Another consideration is what colour you want to use for your crevices. The obvious choice is grey/black, and that'll give you a whit-ish looking white, but you could also use something like Deneb Stone or bone colour which gives a slightly more dusty look. That's what I use for my Bretonnian Knights Templar. White undercoat, 50/50 mix of Deneb/White into the shadowy areas, then pure Deneb stone in the deeper crevices, followed by mixing a touch of Khemri Brown into Deneb stone which I only paint into the deepest crevices. The model still looks "white", but it's a different "white" compared to using light grey or black as the shading. I think it better suits the look of the Knights, but keep in mind there are alternatives to just grey shaded white. Another consideration might be using something like Space Wolves Grey for the shading (maybe with a touch of shadow grey for the deepest of deep crevices). Because SW Grey is a blue-ish grey, using it for shading of white gives a slightly more pure and almost "angelic" look. That's what I use for my Pegasus Knights, as I want them to look pure and clean compared to the Knights running around on the ground.

This seems to be the easiest way I have ever came across but I haven't tried it myself yet:
http://fromthewarp.blogspot.co.uk/2011/12/white-scars-and-how-to-paint-white.html

This tutorial works well
http://fromthewarp.blogspot.com/2011/12/white-scars-and-how-to-paint-white.html

There are a lot of good techniques for painting white, but they are all guided by the same principal; you have to be patient with white.Across large areas, you will never be able to cover with one coat. To get a smooth, even white that won't fill in any detail, you have to layer multiple coats. Starting with a base coat closer to white will make the process quicker.

A couple of good suggestions have already been made, and here's my technique:

Start with a base coat of codex gray (if you're using the new colors, you'll have to look up the new versions), then layer on 50/50 mix codex and fortress grey, leaving the previous layer in just the deepest recesses. Move to straight fortress grey, again creating a gradient with the previous layer. Next is 50/50 fortress grey and skull white, followed by straight skull white. "Painting up to white" is a bit more time consuming, but will give you nice transitions for your shading, which, as previously stated, is important as you have no high lights.

love the tutorials, i think ive got the idea figured out in my head, now to just try it, thanks