It is not Shinjuku Station (M-08) but Shinjuku-sanchome Station (M-09, F-13) which is closest to Isetan Shinjuku Store among Tokyo Metro Stations.
(Shinjuku Station (M-08) does not have Exit B5.)
Also Shinjuku-sanchome Station (S-02) of Toei subway is close.
And how to walk? From what station and by which line will you come to Shinjuku Station?
Shinjuku and Shinjuku-nishiguchi Stations (of five railroad operators) exist in a huge complex, which may well be a labyrinth for first-time visitors.
So, in order to avoid a risk of misleading you, you railroad line needs to be specified.
- JR-East: Shinjuku Station
https://www.jreast.co.jp/e/stations/e866.html: In the map on this page, the north is roughly to the right.
If you come to Shinjuku Station by a JR line,
you can go down from (around) the north end of the platform to the underground concourse,
pass through East Gate,
go up to the 1st floor (= the ground floor),
get out via East Exit, turn to the right (=the south),
go for about 30 meters, take the crosswalk to the left
and follow this route shown by Google Maps for about 290 meters to Isetan Shinjuku Store.
https://www.google.co.jp/maps/dir/35.6912046,139.7015616/35.6912857,13...