Downloaded g++ 4.8 from the PPA but can't set it as default?

You need to let update-alternatives to know that you have 2 C++ compilers, create a record for each one, and then configure which one you want to use. This is done with the following:

sudo update-alternatives --install /usr/bin/g++ g++ /usr/bin/g++-4.6.3 60
sudo update-alternatives --install /usr/bin/g++ g++ /usr/bin/g++-4.8 40
sudo update-alternatives --config g++ 

From this point forward, the only thing required when switching compilers is this command:

sudo update-alternatives --config g++

See man update-alternatives for more info.

^{Source: How to use multiple instances of gcc?}

First of all, you must discover where are your 4.8 binaries of all the tools:

$ which gcc-4.8
/usr/bin/gcc-4.8
$ which g++-4.8
/usr/bin/g++-4.8
$ ls /usr/bin/*-4.8
/usr/bin/cpp-4.8         /usr/bin/x86_64-linux-gnu-cpp-4.8
/usr/bin/g++-4.8         /usr/bin/x86_64-linux-gnu-g++-4.8
/usr/bin/gcc-4.8         /usr/bin/x86_64-linux-gnu-gcc-4.8
/usr/bin/gcc-ar-4.8      /usr/bin/x86_64-linux-gnu-gcc-ar-4.8
/usr/bin/gcc-nm-4.8      /usr/bin/x86_64-linux-gnu-gcc-nm-4.8
/usr/bin/gcc-ranlib-4.8  /usr/bin/x86_64-linux-gnu-gcc-ranlib-4.8
/usr/bin/gcov-4.8

So, we have all our binaries, now lets see if some symlinks are available for such binaries:

$ cd /usr/bin
$ ls -l gcc* cpp g++
lrwxrwxrwx 1 root root      7 sep 18 14:02 cpp -> cpp-4.7
lrwxrwxrwx 1 root root      7 abr 22  2013 g++ -> g++-4.7
lrwxrwxrwx 1 root root      7 sep 18 14:02 gcc -> gcc-4.7

As we can see, only cpp, g++ and gcc has symbolic links. We have two options here.

Symlinking

We replace the symlinks with ours, removing the actuals first:

sudo rm /usr/bin/cpp /usr/bin/gcc /usr/bin/g++

Then creating ours

sudo ln -s /usr/bin/cpp-4.8 /usr/bin/cpp
sudo ln -s /usr/bin/gcc-4.8 /usr/bin/gcc
sudo ln -s /usr/bin/g++-4.8 /usr/bin/g++

To revert it back use the same commands but with 4.7 or 4.6 instead

sudo rm /usr/bin/cpp /usr/bin/gcc /usr/bin/g++
sudo ln -s /usr/bin/cpp-4.7 /usr/bin/cpp
sudo ln -s /usr/bin/gcc-4.7 /usr/bin/gcc
sudo ln -s /usr/bin/g++-4.7 /usr/bin/g++

This is the great description and step-by-step instruction how to create and manage master and slave (gcc and g++) alternatives.

Shortly, it's

sudo update-alternatives --install /usr/bin/gcc gcc /usr/bin/gcc-4.7 60 --slave /usr/bin/g++ g++ /usr/bin/g++-4.7 
sudo update-alternatives --install /usr/bin/gcc gcc /usr/bin/gcc-4.8 40 --slave /usr/bin/g++ g++ /usr/bin/g++-4.8 
sudo update-alternatives --config gcc